2-and 2,5-substituted phenylketoenols

ABSTRACT

The invention relates to novel phenyl-substituted cyclic ketoenols of the formula (I)                    
     in which 
     Het represents one of the groups                    
      in which A, B, D, G, X and Z are each as defined in the description, to a plurality of processes and intermediates for their preparation, and to their use as pesticides.

This is a Divisional Application of Ser. No. 09/230,653 filed Jan. 28,1999, U.S. Pat. No. 6,114,374 which is a 371 of PCT/EP97/03973 Jul. 23,1997.

The invention relates to novel phenyl-substituted cyclic ketoenols, to aplurality of processes and intermediates for their preparation and totheir use as pesticides.

It has already been disclosed that certain phenyl-substituted cyclicketoenols are active as insecticides, acaricides and/or herbicides.

Also known are 1H-arylpyrrolidine-dione derivatives (EP-A-456 063,EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, DE 44 40 594, WO94/01 997, WO 95/01 358, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO96/25 395, WO 96/35 664, WO 97/01 535 and WO 97/02 243).

It is known that certain substituted Δ³-dihydrofuran-2-one derivativeshave herbicidal properties (cf. DE-A-4 014 420). The synthesis of thetetronic acid derivatives used as starting materials (such as, forexample,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³-dihydrofuran-2-one)is likewise described in DE-A-4 014 420. Compounds of similar structurewithout details of an insecticidal and/or acaricidal activity are knownfrom the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1,1985, (8) 1567-76. Furthermore, 3-aryl-Δ³-dihydrofuranone derivativeshaving herbicidal, acaricidal and insecticial properties are disclosedin EP-A-528 156, EP-A 0 647 637, WO 95/26345, WO 96/20 196, WO 96/25395, WO 96/35 664, WO 97/01 535 and WO 97/02 243.

Certain phenyl-pyrone derivatives unsubstitued in the phenyl ring havealready been disclosed (cf. A. M. Chirazi, T. Kappe and E. Ziegler,Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K. Heidenbluth, Chem.Ber. 91, 2849), a possible utility for these compounds as pesticides notbeing indicated. Phenyl-pyrone derivatives substituted in the phenylring and having herbicidal, acaricidal and insecticidal properties aredescribed in EP-A-588 137, WO 96/25 395, WO 96/35 664, WO 97/01 535 andWO 97/02 243.

However, the acaricidal and insecticidal activity and/or spectrum ofaction, and/or the toleration of the known compounds by plants, inparticular by crops, is not always satisfactory.

The invention, accordingly, provides compounds of the formula (I)

in which

X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, benzyloxy,halogenoalkyl, halogenoalkoxy, cyano or nitro,

Z represents hydrogen, amino, halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, hydroxyl, cyano, nitro or respectively optionallysubstituted phenoxy, phenylthio, 5- or 6-membered hetaryloxy, 5- or6-membered hetarylthio, phenylalkyloxy or phenylalkylthio and

Het represents one of the groups

 in which

A represents a respectively optionally substituted radical from thegroup consisting of alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl andalkylthioalkyl, represents respectively saturated or unsaturated andoptionally substituted cycloalkyl or heterocyclyl or representsrespectively optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-,halogenoalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,

B represents alkyl or alkoxyalkyl or

A and B together with the carbon atom that they are attached torepresent a saturated or unsaturated, optionally substituted carbocycleor heterocycle,

D represents hydrogen or represents an optionally substituted radicalfrom the group consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl,polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl,saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl orhetaryl or

A and D together with the atoms that they are attached to represent arespectively optionally substituted carbocycle or heterocycle,

G represents hydrogen (a) or represents one of the groups

 in which

E represents a metal ion equivalent or an ammonium ion,

L represents oxygen or sulphur,

M represents oxygen or sulphur,

R¹ represents respectively optionally halogen-substituted alkyl,alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or representsrespectively optionally halogen-, alkyl- or alkoxy-substitutedcycloalkyl or heterocyclyl or represents respectively optionallysubstituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl orhetaryloxyalkyl,

R² represents respectively optionally halogen-substituted alkyl,alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents respectivelyoptionally substituted cycloalkyl, phenyl or benzyl,

R³, R⁴ and R⁵ independently of one another each represent respectivelyoptionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino,alkylthio, alkenylthio or cycloalkylthio or represent respectivelyoptionally substituted phenyl, benzyl, phenoxy or phenylthio,

R⁶ and R⁷ independently of one another each represent hydrogen,represent respectively optionally halogen-substituted alkyl, cycloalkyl,alkenyl, alkoxy, alkoxyalkyl, represent respectively optionallysubstituted phenyl or benzyl, or form together with the nitrogen atomthat they are attached to an optionally oxygen- or sulphur-containing,optionally substituted cycle.

The compounds of the formula (I) can also be present, depending on thenature of the substituents, as geometric and/or optical isomers andisomer mixtures of differing composition which, if appropriate, can beseparated in a customary manner. Both the pure isomers and the isomermixtures, their preparation and use, and compositions comprising themare part of the subject matter of the present invention. In thefollowing, for simplicity, however, compounds of the formula (I) arealways referred to, although both pure compounds and, if appropriate,mixtures having different proportions of isomer compounds are intended.

Including the meanings (1) to (4) of the group Het, the followingprincipal structures (I-1) to (I-4) result:

in which

A, B, D, G, X and Z are each as defined above.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-1-a) to (I-1-g)result if Het represents the group (1)

in which

A, B, E, L, M, X, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each as definedabove.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-2-a) to (I-2-g)result if Het represents the group (2)

in which

A, B, E, L, M, X, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each as definedabove.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-3-a) to (I-3-g)result if Het represents the group (3)

in which

A, B, E, L, M, X, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each as definedabove.

Depending on the position of the substituent G, the compounds of theformula (I-4) can be present in the two isomeric forms of formulae(I-4)_(a) and (I-4)_(b)

which is intended to be expressed by the dashed line in the formula(I-4).

The compounds of the formulae (I-4)_(a) and (I-4)_(b) can be presentboth as mixtures and in the form of their pure isomers. Mixtures of thecompounds of the formulae (I-4)_(a) and (I-4)_(b) can, if desired, beseparated by physical methods in a manner known per se, for example bychromatographic methods.

For better clarity, in the following in each case only one of thepossible isomers is shown. This does not exclude the possibility thatthe compounds can optionally be present in the form of the isomermixtures or in the other respective isomer form.

Including the various meanings (a), (b), (c), (d), (e), (f) and (g) ofthe group G, the following principal structures (I-4-a) to (I-4-g)result if Het represents the group (4)

in which

A, D, E, L, M, X, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are each as definedabove.

Furthermore, it has been found that the novel compounds of the formula(I) are obtained by one of the processes described below:

(A) Compounds of the formula (I-1-a)

in which

A, B, X and Z are each as defined above, are obtained by theintramolecular condensation of compounds of the formula (II)

 in which

A, B, X and Z are each as defined above, and

R⁸ represents alkyl (preferably C₁-C₆-alkyl),

in the presence of a diluent and in the presence of a base.

(B) Furthermore, it was found that compounds of the formula (I-2-a)

in which

A, B, X and Z are each as defined above, are obtained by theintramolecular condensation of compounds of the formula (III)

 in which

A, B, X, Z and R⁸ are each as defined above, in the presence of adiluent and in the presence of a base.

(C) Furthermore, it was found that compounds of the formula (I-3-a)

in which

A, B, X and Z are each as defined above, are obtained by theintramolecular cyclization of compounds of the formula (IV)

 in which

A, B, X, Z and R⁸ are each as defined above and

W represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl) or alkoxy(preferably C₁-C₈-alkoxy), if appropriate in the presence of a diluentand in the presence of an acid.

(D) Furthermore, it was found that compounds of the formula (I-4-a)

in which

A, D, X and Z are each as defined above, are obtained by reactingcompounds of the formula (V)

 in which

A and D are each as defined above, or their silyl enol ethers of theformula (Va)

 in which

A and D are each as defined above and

R⁸ represents alkyl (preferably methyl), with compounds of the formula(VI)

 in which

X and Z are each as defined above and

Hal represents halogen (preferably chlorine or bromine), if appropriatein the presence of a diluent and if appropriate in the presence of anacid acceptor.

Furthermore, it was found

(E) that the compounds of the formulae (I-1-b) to (I-4-b) shown above inwhich A, B, D, R¹, X and Z are each as defined above are obtained byreacting compounds of the formulae (I-1-a) to (I-4-a) shown above inwhich A, B, D, X and Z are each as defined above

α) with acid halides of the formula (VII)

 in which

R¹ is as defined above and

Hal represents halogen (in particular chlorine or bromine), or

β) with carboxylic anhydrides of the formula (VIII)

R¹—CO—O—CO—R¹  (VIII)

 in which

R¹ is as defined above, if appropriate in the presence of a diluent andif appropriate in the presence of an acid-binding agent;

(F) that the compounds of the formulae (I-1-c) to (I-4-c) shown above inwhich A, B, D, R², M, X and Z are each as defined above and L representsoxygen are obtained by reacting compounds of the formulae (I-1-a) to(I-4-a) shown above in which A, B, D, X and Z are each as defined above,in each case with chloroformic esters or chloroformic thioesters of theformula (IX)

R²—M—CO—Cl  (IX)

 in which

R² and M are each as defined above, if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent;

(G) that compounds of the formulae (I-1-c) to (I-4-c) shown above inwhich A, B, D, R², M, X and Z are each as defined above and L representssulphur are obtained by reacting compounds of the formulae (I-1-a) to(I-4-a) shown above in which A, B, D, X and Z are each as defined above,in each case with chloromonothioformic esters or chlorodithioformicesters of the formula (X)

 in which

M and R² are each as defined above, if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent,

(H) that compounds of the formulae (I-1-d) to (I-4-d) shown above inwhich A, B, D, R³, X and Z are each as defined above are obtained byreacting compounds of the formulae (I-1-a) to (I-4-a) shown above inwhich A, B, D, X and Z are each as defined above, in each case withsulphonyl chlorides of the formula (XII)

R³—SO₂—Cl  (XII)

 in which

R³ is as defined above, if appropriate in the presence of a diluent andif appropriate in the presence of an acid-binding agent,

(I) that compounds of the formulae (I-1-e) to (I-4-e) shown above inwhich A, B, D, L, R⁴, R⁵, X and Z are each as defined above are obtainedby reacting compounds of the formulae (I-1-a) to (I-4-a) shown above inwhich A, B, D, X and Z are each as defined above, in each case withphosphorus compounds of the formula (XIII)

 in which

L, R⁴ and R⁵ are each as defined above and

Hal represents halogen (in particular chlorine or bromine), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent,

(J) that compounds of the formulae (I-1-f) to (I-4-f) shown above inwhich A, B, D, E, X and Z are each as defined above are obtained byreacting compounds of the formulae (I-1-a) to (I-4-a) in which A, B, D,X and Z are each as defined above, in each case with metal compounds oramines of the formulae (XIV) or (XV)

 in which

Me represents a mono- or divalent metal (preferably an alkali metal oralkaline earth metal, such as lithium, sodium, potassium, magnesium orcalcium),

t represents the number 1 or 2 and

R¹⁰, R¹¹, R¹² independently of one another each represent hydrogen oralkyl (preferably C₁-C₈-alkyl), if appropriate in the presence of adiluent;

(K) that compounds of the formulae (I-1-g) to (I-4-g) shown above inwhich A, B, D, L, R⁶, R⁷, X and Z are each as defined above are obtainedby reacting compounds of the formulae (I-1-a) to (I-4-a) shown above inwhich A, B, D, X and Z are each as defined above, in each case

α) with isocyanates or isothiocyanates of the formula (XVI)

R⁶—N═C═L  (XVI)

 in which

R⁶ and L are each as defined above, if appropriate in the presence of adiluent and if appropriate in the presence of a catalyst, or

β) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula(XVII)

 in which

L, R⁶ and R⁷ are each as defined above, if appropriate in the presenceof a diluent and if appropriate in the presence of an acid-bindingagent.

Furthermore, it has been found that the novel compounds of the formula(I) have a very good activity as pesticides, preferably as insecticidesand acaricides, and that they additionally are very well tolerated byplants, in particular by crops.

Formula (I) provides a general definition of the compounds according tothe invention. Preferred substituents or ranges of the radicals shown inthe formulae mentioned hereinabove and hereinbelow are illustratedbelow:

X preferably represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C₁-C₆-alkoxy, benzyloxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, cyano or nitro.

Z preferably represents hydrogen, amino, halogen, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, hydroxyl,cyano, nitro or respectively optionally halogen-, C₁-C₄-alkyl-,C₁-C₄-alkoxy-, C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, nitro- orcyano-substituted phenoxy phenylthio, thiazolyloxy, pyridinyloxy,pyrimidinyloxy, pyrazolyloxy, phenyl-C₁-C₄-alkyloxy orphenyl-C₁-C₇-alkylthio.

Het preferably represents one of the groups

A preferably represents respectively optionally halogen-substitutedC₁-C₁₂-alkyl, C₂-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-aklyl,poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or C₁-C₁₀-alkylthio-C₁-C₆-alkyl,preferably represents optionally halogen-, C₁-C₆-alkyl- orC₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in which optionally one or twonot directly adjacent methylene groups are replaced by oxygen and/orsulphur, or preferably represents respectively optionally halogen-,C₁-C₆-alkyl-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-,C₁-C₆-halogenoalkoxy-, cyano- or nitro-substituted phenyl, naphthyl,phenyl-C₁-C₆-alkyl, naphthyl-C₁-C₆-alkyl or hetaryl having 5 or 6 ringatoms and one to three hetero atoms from the group consisting of oxygen,sulphur and nitrogen (in particular from the group consisting offuranyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyland thienyl).

B preferably represents C₁-C₁₂-alkyl or C₁-C₈-alkoxy-C₁-C₆-alkyl or

A, B and the carbon atom that they are attached to preferably representC₃-C₁₀-cycloalkyl or C₅-C₁₀-cycloalkenyl where in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,C₁-C₈-halogenoalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl or

A, B and the carbon atom that they are attached to preferably representC₅-C₆-cycloalkyl which is substituted by an alkylenediyl groupoptionally containing one or two not directly adjacent oxygen and/orsulphur atoms, or by an alkylenedioxy group or an alkylenedithioyl groupforming a further five- to eight-membered ring with the carbon atom thatit is attached to, or

A, B and the carbon atom that they are attached to preferably representC₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which two carbon atoms arelinked to each other by respectively optionally C₁-C₆-alkyl-,C₁-C₆-alkoxy- or halogen-substituted C₃-C₆-alkanediyl, C₃-C₆-alkenediylor C₄-C₆-alkanedienediyl, one methylene group in each case beingoptionally replaced by oxygen or sulphur.

D preferably represents hydrogen, preferably represents respectivelyoptionally halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl,C₃-C₈-alkynyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkylor C₁-C₁₀-alkylthio-C₂-C₈-alkyl, preferably represents optionallyhalogen-, C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₄-halogenoalkyl-substitutedC₃-C₈-cycloalkyl in which optionally one or two not directly adjacentmethylene groups are replaced by oxygen and/or sulphur, or preferablyrepresents respectively optionally halogen-, C₁-C₆ alkyl-,C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-, C₁-C₆-halogenoalkoxy-, cyano- ornitro-substituted phenyl, hetaryl having 5 or 6 ring atoms and one ortwo hetero atoms from the group consisting of oxygen, sulphur andnitrogen (in particular from the group consisting of furanyl,imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyland triazolyl), phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl having 5 or 6ring atoms and one or two hetero atoms from the group consisting ofoxygen, sulphur and nitrogen (in particular from the group consisting offuranyl-, imidazolyl-, pyridyl-, thiazolyl-, pyrazolyl-, pyrimidyl-,pyrrolyl-, thienyl- and triazolyl-C₁-C₆-alkyl) or

A and D together preferably represent a C₃-C₆-alkanediyl,C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group in which respectivelyoptionally one methylene group is replaced by oxygen or sulphur andwhich are respectively optionally substituted by halogen or respectivelyoptionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy,C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy or by a furtherC₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group forminga fused ring, in which optionally respectively one methylene group isreplaced by oxygen or sulphur and which are optionally substituted byC₁-C₆-alkyl, or

A and D together represent a C₃-C₆-alkanediyl or C₃-C₆-alkenediyl groupcontaining in each case optionally one of the following groups

G preferably represents hydrogen (a) or represents one of the groups

 in which

E represents a metal ion equivalent or an ammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ preferably represents respectively optionally halogen-substitutedC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl,C₁-C₈-alkylthio-C₁-C₈-alkyl or poly-C₁-C₈-alkoxy-C₁-C₈-alkyl orpreferably represents optionally halogen-, C₁-C₆-alkyl- orC₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in which optionally one or twonot directly adjacent methylene groups are replaced by oxygen and/orsulphur,

preferably represents optionally halogen-, cyano-, nitro-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl-, C₁-C₆-halogenoalkoxy-,C₁-C₆-alkylthio- or C₁-C₆-alkylsulphonyl-substituted phenyl,

preferably represents optionally halogen-, nitro-, cyano-, C₁-C₆-alkyl,C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substitutedphenyl-C₁-C₆-alkyl,

preferably represents optionally halogen- or C₁-C₆-alkyl-substituted 5-or 6-membered hetaryl having one or two hetero atoms from the groupconsisting of oxygen, sulphur and nitrogen (in particular from the groupconsisting of pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl andthienyl),

preferably represents optionally halogen- or C₁-C₆-alkyl-substitutedphenoxy-C₁-C₆-alkyl or

preferably represents optionally halogen-, amino- orC₁-C₆-alkyl-substituted 5- or 6-membered hetaryloxy-C₁-C₆-alkyl havingone or two hetero atoms from the group consisting of oxygen, sulphur andnitrogen (in particular from the group consisting ofpyridyloxy-C₁-C₆-alkyl, pyrimidyloxy-C₁-C₆-alkyl andthiazolyloxy-C₁-C₆-alkyl).

R² preferably represents respectively optionally halogen-substitutedC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl orpoly-C₁-C₈-alkoxy-C₂-C₈-alkyl,

preferably represents optionally halogen-, C₁-C₆-alkyl- orC₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl or

preferably represents respectively optionally halogen-, cyano-, nitro-,C₁-C₆alkyl-, C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- orC₁-C₆-halogenoalkoxy-substituted phenyl or benzyl.

R³ preferably represents optionally halogen-substituted C₁-C₈-alkyl orrespectively optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, cyano- or nitro-substitutedphenyl or benzyl.

R⁴ and R⁵ independently of one another each preferably representrespectively optionally halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy,C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)-amino, C₁-C₈-alkylthio orC₃-C₈-alkenylthio or preferably represent respectively optionallyhalogen-, nitro-, cyano-, C₁-C₄-alkoxy-, C₁-C₄-halogenoalkoxy-,C₁-C₄-alkylthio-, C₁-C₄-halogeno-alkylthio-, C₁-C₄-alkyl- orC₁-C₄-halogenoalkyl-substituted phenyl,phenoxy or phenylthio.

R⁶ and R⁷ independently of one another each preferably representhydrogen, preferably represent respectively optionallyhalogen-substituted C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy,C₃-C₈-alkenyl or C₁-C₈-alkoxy -C₂-C ₈-alkyl, preferably representrespectively optionally halogen-, C₁-C₈-alkyl-, C₁-C₈-halogenoalkyl- orC₁-C₈-alkoxy-substituted phenyl or benzyl or together preferablyrepresent an optionally C₁-C₆-alkyl-substituted C₃-C₆-alkylene radicalin which optionally one methylene group is replaced by oxygen orsulphur.

R¹³ preferably represents hydrogen or respectively optionallyhalogen-substituted C₁-C₈-alkyl or C₁-C₈-alkoxy, preferably representsoptionally halogen-, C₁-C₄-alkyl- or C₁-C₄-alkoxy-substitutedC₃-C₈-cycloalkyl in which optionally one methylene group is replaced byoxygen or sulphur, or preferably represents respectively optionallyhalogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₄-halogenoalkyl-,C₁-C₄-halogenoalkoxy-, nitro- or cyano-substituted phenyl,phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄-alkoxy.

R¹⁴ preferably represents hydrogen or C₁-C₈-alkyl or

R¹³ and R¹⁴ together preferably represent C₄-C₆-alkanediyl.

R¹⁵ and R¹⁶ are identical or different and each preferably representC₁-C₆-alkyl or

R¹⁵ and R¹⁶ together preferably represent a C₂-C₄-alkanediyl radicalwhich is optionally substituted by C₁-C₆-alkyl or by optionallyhalogen-, C₁-C₄-alkyl-, C₁C₄-halogenoalkyl-, C₁-C₄-alkoxy-,C₁-C₄-halogenoalkoxy-, nitro-or cyano-substituted phenyl.

R¹⁷ and R¹⁸ independently of one another each preferably representhydrogen, preferably represent optionally halogen-substitutedC₁-C₈-alkyl or preferably represent optionally halogen-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₄-halogenoalkyl-, C₁-C₄-halogenoalkoxy-, nitro- orcyano-substituted phenyl or

R¹⁷ and R¹⁸ together with the carbon atom that they are attached topreferably represent optionally C₁-C₄-alkyl-substituted C₅-C₇-cycloalkylin which optionally one methylene group is replaced by oxygen orsulphur.

R¹⁹ and R²⁰ independently of one another each preferably representC₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino,C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)-amino ordi-(C₃-C₁₀-alkenyl)-amino.

X particularly preferably represents fluorine, chlorine, bromine,C₁-C₄-alkyl, C₁-C₄-alkoxy, benzyloxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro.

Z particularly preferably represents hydrogen, amino, fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, hydroxyl, cyano, nitro or respectively optionallyfluorine-, chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,C₁-C₂-halogenoalkyl-, C₁-C₂-halogenoalkoxy-, nitro- or cyano-substitutedphenoxy or benzyloxy.

Het particularly preferably represents one of the groups

A particularly preferably represents respectively optionally fluorine-or chlorine-substituted C₁-C₁₀-alkyl, C₂-C₆-alkenyl,C₁-C₈-alkoxy-C₁-C₆-alkyl, poly-C₁-C₆-alkoxy-C₁-C₆-alkyl orC₁-C₈-alkylthio-C₁-C₆-alkyl or particularly preferably representsoptionally fluorine-, chlorine-, C₁-C₄-alkyl- orC₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl in which optionally one or twonot directly adjacent methylene groups are replaced by oxygen and/orsulphur, or particularly preferably represents respectively optionallyfluorine-, chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-halogenoalkyl-,C₁-C₄-alkoxy-, C₁-C₄-halogenoalkoxy-, cyano, or nitro-substitutedphenyl, furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl,thiazolyl, thienyl or phenyl-C₁-C₄-alkyl.

B particularly preferably represents C₁-C₁₀-alkyl orC₁-C₆-alkoxy-C₁-C₄-alkyl or

A, B and the carbon atom that they are attached to particularlypreferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl where onemethylene group in each case is optionally replaced by oxygen or sulphurand which are optionally substituted by C₁-C₆-alkyl, C₃-C₈-cycloalkyl,C₁-C₃-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorineor phenyl or

A, B and the carbon atom that they are attached to particularlypreferably represent C₅-C₆-cycloalkyl which is substituted by analkylenediyl group optionally containing one or two not directlyadjacent oxygen or sulphur atoms or by an alkylenedioxy group or by analkylenedithiol group which forms together with the carbon atom that itis attached to a further five- to seven-membered ring or

A, B and the carbon atom that they are attached to particularlypreferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloaikenyl in which twocarbon atoms are linked to each other by respectively optionallyC₁-C₄-alkyl-, C₁-C₄-alkoxy-, fluorine-, chlorine- or bromine-substitutedC₃-C₅-alkanediyl or C₃-C₅-alkenediyl, one methylene group in each casebeing optionally replaced by oxygen or sulphur, or are linked to eachother by butadienediyl.

D particularly preferably represents hydrogen, particularly preferablyrepresents respectively optionally fluorine- or chlorine-substitutedC₁-C₆-alkyl or C₁-C₆-alkoxy, particularly preferably representsoptionally fluorine-, chlorine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy- orC₁-C₂-halogenoalkyl-substituted C₃-C₇-cycloalkyl in which optionally oneor two not directly adjacent methylene groups are replaced by oxygenand/or sulphur, or particularly preferably represents respectivelyoptionally fluorine-, chlorine-, bromine-, C₁-C₂-alkyl-,C₁-C₂-halogenoalkyl, C₁-C₂-alkoxy-, C₁-C₂-halogenoalkoxy-, cyano- ornitro-substituted phenyl, furanyl, imidazolyl, pyridyl, thiazolyl,pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or phenyl-C₁-C₂-alkylor

A and D together particularly preferably represent a C₃-C₈-alkanediyl orC₃-C₅-alkenediyl group in which in each case one methylene group isoptionally replaced by oxygen or sulphur and which are optionallysubstituted by fluorine, chlorine or by respectively optionallyfluorine- or chlorine-substituted C₁-C₆-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylthio. C₃-C₆-cycloalkyl, phenyl or benzyloxy or

 in which in each case optionally one of the following groups iscontained:

G particularly preferably represents hydrogen (a) or represents one ofthe groups

 in which

E represents a metal ion equivalent or an ammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ particularly preferably represents respectively optionally fluorine-or chlorine-substituted C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl orpoly-C₁-C₆-alkoxy-C₁-C₆-alkyl or particularly preferably representsoptionally fluorine-, chlorine-, C₁-C₅-alkyl- orC₁-C₅-alkoxy-substituted C₃-C₇-cycloalkyl in which optionally one or twonot directly adjacent methylene groups are replaced by oxygen and/orsulphur,

particularly preferably represents optionally fluorine-, chlorine-,bromine-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,C₁-C₃-halogenoalkyl-, C₁-C₃-halogenoalkoxy-, C₁-C₄-alkylthio- orC₁-C₄-alkylsulphonyl-substituted phenyl,

particularly preferably represents optionally fluorine-, chlorine-,bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₃-halogenoalkyl- orC₁-C₃-halogenoalkoxy-substituted phenyl-C₁-C₄-alkyl,

particularly preferably represents respectively optionally fluorine-,chlorine-, bromine- or C₁-C₄-alkyl-substituted pyrazolyl, thiazolyl,pyridyl, pyrimidyl, furanyl or thienyl,

particularly preferably represents optionally fluorine-, chlorine-,bromine- or C₁-C₄-alkyl-substituted phenoxy-C₁-C₅-alkyl or

particularly preferably represents respectively optionally fluorine-,chlorine-, bromine-, amino- or C₁-C₄-alkyl-substitutedpyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl orthiazolyloxy-C₁-C₅-alkyl.

R² particularly preferably represents respectively optionally fluorine-or chlorine-substituted C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl,C₁-C₆-alkoxy-C₂-C₆-alkyl or poly-C₁-C₆-alkoxy-C₂-C₆-alkyl,

particularly preferably represents optionally fluorine-, chlorine-,C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl or

particularly preferably represents respectively optionally fluorine-,chlorine-, bromine-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₃-alkoxy-,C₁-C₃-halogenoalkyl- or C₁-C₃-halogenoalkoxy-substituted phenyl orbenzyl.

R³ particularly preferably represents optionally fluorine- orchlorine-substituted C₁-C₆-alkyl or respectively optionally fluorine-,chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₂-halogenoalkoxy-,C₁-C₂-halogenoalkyl-, cyano-, or nitro-substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another each particularly preferablyrepresent respectively optionally fluorine- or chlorine-substitutedC₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)-amino,C₁-C₆-alkylthio or C₃-C₄-alkenylthio or particularly preferablyrepresent respectively optionally fluorine-, chlorine-, bromine-,nitro-, cyano-, C₁-C₃-alkoxy-, C₁-C₃-haloge-noalkoxy-, C₁-C₃-alkylthio-,C₁-C₃-halogenoalkylthio-, C₁-C₃alkyl- or C₁-C₃-halogenoalkyl-substitutedphenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another each particularly preferablyrepresent hydrogen, particularly preferably represent respectivelyoptionally fluorine -or chlorine-substituted C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl orC₁-C₆-alkoxy-C₂-C₆-alkyl, particularly preferably represent respectivelyoptionally fluorine-, chlorine-, bromine-, C₁-C₅-halogenoalkyl-,C₁-C₅-alkyl- or C₁-C₅-alkoxy-substituted phenyl or benzyl, or togetherparticularly preferably represent an optionally C₁-C₄-alkyl-substitutedC₃-C₆-alkylene radical in which optionally one methylene group isreplaced by oxygen or sulphur.

R¹³ particularly preferably represents hydrogen or respectivelyoptionally fluorine- or chlorine-substituted C₁-C₆-alkyl orC₁-C₆-alkoxy, particularly preferably represents optionally fluorine-,C₁-C₂-alkyl- or C₁-C₂-alkoxy-substituted C₃-C₇-cycloalkyl in whichoptionally one methylene group is replaced by oxygen or sulphur, orparticularly preferably represents respectively optionally fluorine-,chlorine-, bromine-, C₁-C₅-alkyl-, C₁-C₅-alkoxy-, C₁-C₂-halogenoalkyl-,C₁-C₂-halogenoalkoxy-, nitro- or cyano-substituted phenyl,phenyl-C₁-C₃-alkyl or phenyl-C₁-C₂-alkyloxy.

R¹⁴ particularly preferably represents hydrogen or C₁-C₆-alkyl or

R¹³ and R¹⁴ together particularly preferably represent C₄-C₆-alkanediyl.

R¹⁵ and R¹⁶ are identical or different and each particularly preferablyrepresent C₁-C₄-alkyl or

R¹⁵ and R¹⁶ together particularly preferably represent aC₂-C₃-alkanediyl radical which is optionally substituted by C₁-C₄-alkylor by optionally fluorine-, chlorine-, bromine-, C₁-C₂-alkyl-,C₁-C₂-halogenoalkyl-, C₁-C₂-alkoxy-, C₁-C₂-halogenoalkoxy-, nitro- orcyano-substituted phenyl.

X very particularly preferably represents fluorine, chlorine, bromine,methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl,methoxy, ethoxy, n-propoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy, cyano or nitro,

Z very particularly preferably represents hydrogen, amino, fluorine,chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy,trifluoromethyl, trifluoro-methoxy, difluoromethoxy, cyano or nitro.

Het very particularly preferably represents one of the groups

A very particularly preferably represents respectively optionallyfluorine- or chlorine-substituted C₁-C₈-alkyl, C₂-C₄-alkenyl,C₁-C₆-alkoxy-C₁-C₄-alkyl, poly-C₁-C₄-alkoxy-C₁-C₄-alkyl orC₁-C₆-alkylthio-C₁-C₄-alkyl, or very particularly preferably representsoptionally fluorine-, chlorine-, methyl- or methoxy-substitutedC₃-C₆-cycloalkyl in which optionally one or two not directly adjacentmethylene groups are replaced by oxygen and/or sulphur, or veryparticularly preferably represents respectively optionally fluorine-,chlorine-, bromine-, methyl-, ethyl-, n-propyl-, iso-propyl-, methoxy-,ethoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- ornitro-substituted phenyl, pyridyl or benzyl.

B very particularly preferably represents C₁-C₈-alkyl orC₁-C₄-alkoxy-C₁-C₂-alkyl or

A, B and the carbon atom that they are attached to very particularlypreferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which ineach case optionally one methylene group is replaced by oxygen orsulphur and which are optionally substituted by methyl, ethyl, n-propyl,iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, cyclohexyl,trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy,iso-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, fluorine,chlorine or phenyl or

A, B and the carbon atom that they are attached to very particularlypreferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which twocarbon atoms are linked together by C₃-C₄-alkanediyl or C₃-C₄-alkenediylin which in each case optionally one methylene group is replaced byoxygen or sulphur, or are linked together by butadienediyl.

D very particularly preferably represents hydrogen, very particularlypreferably represents respectively optionally fluorine-substitutedC₁-C₄-alkyl or C₁-C₄-alkoxy or C₃-C₆-cycloalkyl in which optionally oneor two not directly adjacent methylene groups are replaced by oxygenand/or sulphur, or very particularly preferably represents respectivelyoptionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, n-propyl-,iso-propyl-, methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-,cyano- or nitro-substituted phenyl, furanyl, pyridyl, thienyl or benzyl,or

A and D together very particularly preferably represent aC₃-C₅-alkanediyl or C₃-C₅-alkenediyl group in which in each caseoptionally one methylene group is replaced by oxygen or sulphur andwhich are optionally substituted by fluorine, chlorine or byrespectively optionally fluorine- or chlorine-substituted C₁-C₆-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxy.

G very particularly preferably represents hydrogen (a) or represents oneof the groups

 in which

E represents a metal ion equivalent or an ammonium ion,

L represents oxygen or sulphur and

M represents oxygen or sulphur.

R¹ very particularly preferably represents respectively optionallyfluorine- or chlorine-substituted C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl,C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl,poly-C₁-C₄-alkoxy-C₁-C₄-alkyl or very particularly preferably representsoptionally fluorine-, chlorine-, methyl-, ethyl-, n-propyl-, i-propyl-,n-butyl-, i-butyl-, tert-butyl-, methoxy-, ethoxy-, n-propoxy- oriso-propoxy-substituted C₃-C₆-cycloalkyl in which optionally one or twonot directly adjacent methylene groups are replaced by oxygen and/orsulphur,

very particularly preferably represents optionally fluorine-, chlorine-,bromine-, cyano-, nitro-, methyl-, ethyl-, n-propyl-, i-propyl-,methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-, methylthio-,ethylthio-, methylsulphonyl- or ethylsulphonyl-substituted phenyl,

very particularly preferably represents optionally fluorine-, chlorine-,bromine-, methyl-, ethyl-, n-propyl-, i-propyl-, methoxy-, ethoxy-,trifluoromethyl- or trifluoromethoxy-substituted benzyl,

very particularly preferably represents respectively optionallyfluorine-, chlorine-, bromine-, methyl- or ethyl-substituted furanyl,thienyl or pyridyl,

very particularly preferably represents optionally fluorine-, chlorine-,methyl- or ethyl-substituted phenoxy-C₁-C₄-alkyl or

very particularly preferably represents respectively optionallyfluorine-, chlorine-, amino-, methyl- or ethyl-substitutedpyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl orthiazolyloxy-C₁-C₄-alkyl

R² very particularly preferably represents respectively optionallyfluorine- or chlorine-substituted C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl,C₁-C₄-alkoxy-C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂-C₆-alkyl,

very particularly preferably represents optionally fluorine-, chlorine-,methyl-, ethyl-, n-propyl-, iso-propyl- or methoxy-substitutedC₃-C₆-cycloalkyl,

or very particularly preferably represents respectively optionallyfluorine-, chlorine-, cyano-, nitro-, methyl-, ethyl-, n-propyl-,i-propyl-, methoxy-, ethoxy-, trifluoromethyl- ortrifluoromethoxy-substituted phenyl or benzy.

R³ very particularly preferably represents optionally fluorine- orchlorine-substituted methyl, ethyl, propyl, iso-propyl, n-butyl,tert-butyl or respectively optionally fluorine-, chlorine-, bromine-,methyl-, ethyl-, iso-propyl-, tert-butyl-, methoxy-, ethoxy-,iso-propoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- ornitro-substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another each very particularly preferablyrepresent respectively optionally fluorine- or chlorine-substitutedC₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)-amino orC₁-C₄-alkylthio or very particularly preferably represent respectivelyoptionally fluorine-, chlorine-, bromine-, nitro-, cyano-, methyl-,methoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl,phenoxy or phenylthio.

R⁶ and R⁷ independently of one another each very particularly preferablyrepresent hydrogen, very particularly preferably represent respectivelyoptionally fluorine- or chlorine-substituted C₁-C₄-alkyl,C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkenyl orC₁-C₄-alkoxy-C₂-C₄-alkyl, very particularly preferably representrespectively optionally fluorine-, chlorine-, bromine-, methyl-,methoxy- or trifluoromethyl-substituted phenyl or benzyl, or togethervery particularly preferably represent an optionally methyl- orethyl-substituted C₅-C₆-alkylene radical in which optionally onemethylene group is replaced by oxygen or sulphur.

Particular preference is given to compounds of the formula (I) in whichZ does not represent hydrogen.

Preference is also given to those compounds where D does not representmethyl.

The abovementioned definitions or illustrations of radicals mentionedgenerally or in preferred ranges can be combined with each other asdesired, i.e. also between the respective ranges and preferred ranges.They apply correspondingly to the final products and to the precursorsand intermediates.

For the purpose of the invention, preference is given to compounds ofthe formula (I) in which there exists a combination of the meaningsmentioned above as preferred (preferably).

For the purpose of the invention, particular preference is given tocompounds of the formula (I) in which there exists a combination of themeanings mentioned above as particularly preferred.

For the purpose of the invention, very particular preference is given tocompounds of the formula (I) in which there exists a combination of themeanings mentioned above as very particularly preferred.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenylcan, as far as possible, in each case be straight-chain or branched,also in combination with hetero atoms, for example in alkoxy.

Optionally substituted radicals can be mono- or polysubstituted, itbeing possible in the case of polysubstitution for the substituents tobe identical or different.

In addition to the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-1-a) may be specificallymentioned:

TABLE 1 X = CH₃; Z = CH₃ A B CH₃ CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉ CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO—C₃H₇—(CH₂)₂— —(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

Table 2

A and B are each as defined in Table 1 with

X=CH₃; Z=Cl

Table 3

A and B are each as defined in Table 1 with

X=Cl; Z=CH₃

In addition to the compounds mentioned in the preparation examples, thefollowing compounds of the formula (I-2-a) may be specificallymentioned:

TABLE 4 X = CH₃; Z = CH₃ A B CH₃ CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉ CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO—C₃H₇—(CH₂)₂— —(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

Table 5

A and B are each as defined in Table 4 with

X=CH₃; Z=Cl

Table 6

A and B are each as defined in Table 4 with

X=Cl; Z=CH₃

In addition to the compounds mentioned in the preparation examples, thefollowing compounds of the formula (I-3-a) may be specificallymentioned:

TABLE 7 X = CH₃; Z = CH₃ A B CH₃ CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉ CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO—C₃H₇—(CH₂)₂— —(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

Table 8

A and B are each as defined in Table 7 with

X=CH₃; Z=Cl

Table 9

A and B are each as defined in Table 7 with

X=Cl; Z=CH₃

In addition to the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-4-a) may be specificallymentioned:

TABLE 10 X = CH₃; Z = CH₃

A D CH₃

CH₃

CH₃

CH₃

CH₃

CH₃

CH₃

CH₃

CH₃ C₅H₉ CH₃ C₃H₅ (CH₂)₃ (CH₂)₄ C(CH₃)₂OC(CH₃)₂

Table 11

A and D are each as defined in Table 10 with

X=CH₃; Z=Cl

Table 12

A and D are each as defined in Table 10 with

X=Cl; Z=CH₃

If according to process (A) ethylN-[(3-chloro-6-methyl)-phenylacetyl]-1amino-4-ethyl-cyclohexane-carboxylateis used as starting material, the course of the process according to theinvention can be represented by the following reaction scheme:

If according to process (B) ethylO-[(2,5-dichloro)-phenylacetyl]-2-hydroxy-isobutyrate is used, thecourse of the process according to the invention can be represented bythe following reaction scheme:

If according to process (C) ethyl2-[(2-chloro-5-methyl)-phenyl]-4-(4-methoxy)benzylmercapto-4-methyl-3-oxo-valerateis used, the course of the process according to the invention can berepresented by the following reaction scheme:

If, for example, according to process (D)(chlorocarbonyl)-2-[(3-chloro-6-methyl)phenyl]-ketene and4-fluoro-propiophenone are used as starting materials, the course of theprocess according to the invention can be represented by the followingreaction scheme:

If according to process (Eα)3-[(2,5-dichloro)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-dione andpivaloyl chloride are used as starting materials, the course of theprocess according to the invention can be represented by the followingreaction scheme:

If according to process (E) (variant β)3-[(2,5-dichloro)-phenyl)]-4-hydroxy-5-methyl-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride are used as starting materials, the course of theprocess according to the invention can be represented by the followingreaction scheme:

If according to process (F)8-[(2-chloro-5-methyl)-phenyl]-5,5-pentamethylenepyrrolidine-2,4-dioneand ethoxyethyl chloroformate are used as starting materials, the courseof the process according to the invention can be represented by thefollowing reaction scheme:

If according to process (G)3-[(2-bromo-5-methyl)-phenyl]-4-hydroxy-5-methyl-6-(3-pyridyl)-pyroneand methyl chloromonothioformate are used as starting materials, thecourse of the reaction can be represented in the following manner:

If according to process (H)2-[(2,5-dimethyl)-phenyl]-5,5-[(3-methyl)-pentamethylene]pyrrolidine-2,4-dioneand methanesulphonyl chloride are used as starting materials, the courseof the reaction can be represented by the following reaction scheme:

If according to process (I)2-[(2-chloro-5-methyl)-phenyl]-4-hydroxy-5-methyl-6-(2-pyridyl)-pyroneand 2,2,2-trifluoroethyl chloromethanethio-phosphonate are used asstarting materials, the course of the reaction can be represented by thefollowing reaction scheme:

If according to process (J)3-[(2,5-dichloro)-phenyl]-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dioneand NaOH are used as components, the course of the process according tothe invention can be represented by the following reaction scheme:

If according to process (K) (variant α)3[(2-chloro-5-methyl)-phenyl]-4-hydroxy-5,5-tetramethylene-Δ³-dihydro-furan-2-oneand ethyl isocyanate are used as starting materials, the course of thereaction can be represented by the following reaction scheme:

If according to process (K) (variant β)3-[(2-chloro-5-methyl)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-dione anddimethylcarbamoyl chloride are used as starting materials, the course ofthe reaction can be represented by the following scheme:

The compounds of the formula (II)

in which

A, B, X, Z and R⁸ are each as defined above, required as startingmaterials in process (A) according to the invention are novel.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XVIII)

in which

A, B and R⁸ are as defined above, are acylated using substitutedphenylacetyl halides of the formula (XIX)

 in which

X and Z are each as defined above and

Hal represents chlorine or bromine, (Chem. Reviews 52, 237-416 (1953);Bhattacharya, Indian J. Chem. 6, 341-5, 1968) or when acylamino acids ofthe formula (XX)

 in which

A, B, X and Z are each as defined above, are esterified (Chem. Ind.(London) 1568 (1968)).

The compounds of the formula (XX)

in which

A, B, X and Z are each as defined above, are novel.

The compounds of the formula (XX) are obtained when amino acids of theformula (XXI)

in which

A and B are each as defined above, are acylated using substitutedphenylacetyl halides of the formula (XIX)

 in which

X and Z are each as defined above and

Hal represents chlorine or bromine, according to Schotten-Baumann(Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1977, p.505).

Some of the compounds of the formula (XlX) are novel. They can beprepared by known methods.

The compounds of the formula (XIX) are obtained, for example, byreacting substituted phenylacetic acids of the formula (XXXII)

in which

X and Z are each as defined above, with halogenating agents (for examplethionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorustrichloride, phosphorus tribromide or phosphorus pentachloride), ifappropriate in the presence of a diluent (for example optionallychlorinated aliphatic or aromatic hydrocarbons such as toluene ormethylene chloride) at temperatures from −20° C. to 150° C., preferablyfrom −10° C. to 100° C.

The compounds of the formula (XXII) are novel with the exception of2,5-dichlorophenylacetic acid (CAS 5398798),5-chloro-2-methoxyphenylacetic acid (CAS 7569-6-22),2-chloro-5-methylphenylacetic acid (CAS 81682-39-5),2,5-difluorophenylacetic acid (CAS 85068-27-5),2-bromo-5-methylphenylacetic acid (BRN 3 249 577) and2-chloro-5-trifluoromethylphenylacetic acid (CAS 22893-39-6), they canbe prepared by methods known from the literature (Organikum, 15thedition, p. 533, VEB Deutscher Verlag der Wissenschaften, Berlin 1977).The compounds of the formula (XXII) are obtained, for example, byhydrolysing substituted phenylacetic acid esters of the formula (XXIII)

in which

X, Z and R⁸ are each as defined above, at temperatures between 0° C. and150° C., preferably between 20° C. and 100° C., in the presence of anacid (for example an inorganic acid such as hydrochloric acid) or of abase (for example of an alkali metal hydroxide such as sodium hydroxideor potassium hydroxide) and, if appropriate, of a diluent (for exampleof an aqueous alcohol such as methanol or ethanol).

The compounds of the formula (XXIII) are novel with the exception ofmethyl 2,5-dichlorophenylacetate (CAS 96129-66-7) and methyl5-chloro-2-methoxy-phenylacetate (CAS 26939-01-5), they can be preparedby methods known in principle.

The compounds of the formula (XXIII) are obtained, for example, byreacting substituted 1,1,1-trichloro-2-phenylethanes of the formula(XXIV)

in which

X and Z are each as defined above, first with alkoxides (for examplealkali metal alkoxides such as sodium methoxide or sodium ethoxide) inthe presence of a diluent (for example the alcohol derived from thealkoxide) at temperatures between 0° C. and 150° C., preferably between20° C. and 120° C., and then reacting with an acid (preferably aninorganic acid, such as sulphuric acid) at temperatures between −20° C.and 150° C., preferably 0° C. and 100° C. (cf. DE 3 314 249).

The compounds of the formula (XXIV) are novel, they can be prepared bymethods known in principle.

The compounds of the formula (XXIV) are obtained, for example, whenanilines of the formula (XXV)

in which

X and Z are as defined above, are reacted with vinylidene chloride(CH₂═CC₂) in the presence of an alkyl nitrite of the formula (XXVI)

R²¹—ONO  (XXVI)

 in which

R²¹ represents alkyl, preferably C₁-C₆-alkyl, in the presence ofcopper(II) chloride and, if appropriate, in the presence of a diluent(for example of an aliphatic nitrile such as acetonitrile) at atemperature of −20° C. to 80° C., preferably 0° C. to 60° C.

The compounds of the formulae (XXV) and (XXVI) are known compounds oforganic chemistry. Copper(II) chloride and vinylidene chloride have longbeen known and are commercially available.

Some of the compounds of the formulae (XVIII) and (XXI) are known and/orthey can be prepared by known processes (see, for example, Compagnon,Miocque Ann. Chim. (Paris) [14]5, p. 11-22, 23-27 (1970)).

The substituted cyclic aminocarboxylic acids of the formula (XXIa), inwhich A and B form a ring, are in general obtainable by theBucherer-Bergs synthesis or by the Strecker synthesis and are in eachcase obtained here in different isomeric forms. Thus, according to theconditions of the Bucherer-Bergs synthesis mainly the isomers (in thefollowing designated as β for the sake of simplicity) in which theradicals R and the carboxyl group are equatorial are obtained, whileaccording to the conditions of the Strecker synthesis mainly the isomers(in the following designated as a for the sake of simplicity) areobtained in which the amino group and the radicals R are equatorial.

Bucherer-Bergs synthesis

(β-isomer)

Strecker synthesis

(α-isomer)

(L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.J. Chem. 53, 3339 (1975).

Furthermore the starting materials of the formula (II)

in which

A, B, X, Z and R⁸ are each as defined above, used in the above process(A) can be prepared by reacting aminonitriles of the formula (XXVII)

 in which

A and B are each as defined above, with substituted phenylacetyl halidesof the formula (XIX)

 in which

X, Z and Hal are each as defined above, to give compounds of the formula(XXVIII)

 in which

A, B, X and Z are each as defined above, and then subjecting these to anacidic alcoholysis.

The compounds of the formula (XXVIII) are also novel.

The compounds of the formula (III)

in which

A, B, X, Z and R⁸ are each as defined above, required as startingmaterials in process (B) according to the invention are novel.

They can be prepared in a simple manner by methods known in principle.

The compounds of the formula (III) are obtained, for example, when2-hydroxycarboxylic acid esters of the formula (XXIX)

in which

A, B and R⁸ are each as defined above, are acylated using substitutedphenylacetyl halides of the formula (XIX)

 in which

X, Z and Hal are each as defined above (Chem. Reviews 52, 237-416(1953)).

The compounds of the formula (IV)

in which

A, B, W, X, Z and R⁸ are each as defined above, required as startingmaterials in the above process (C) are novel.

They can be prepared by methods known in principle.

The compounds of the formula (IV) are obtained for example, whensubstituted phenylacetic acid esters of the formula (XXIII)

in which

X, R⁸ and Z are each as defined above, are acylated using2-benzylthio-carbonyl halides of the formula (XXX)

 in which

A, B and W are each as defined above and

Hal represents halogen (in particular chlorine or bromine), in thepresence of strong bases (see, for example, M. S. Chambers, E. J.Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).

The benzylthio-carbonyl halides of the formula (XXX) are known in somecases and/or can be prepared by known methods (J. Antibiotics (1983),26, 1589).

The halogenocarbonylketenes of the formula (VI) in which Z does notrepresent hydrogen, which are required as starting materials in process(D), are novel. They can be prepared in a simple manner by methods knownin principle (cf., for example, Org. Prep. Proced. Int., 7, (4),155-158, 1975 and DE 1 945 703).

The compounds of the formula (VI)

in which

X and Z are each as defined above and

Hal represents chlorine or bromine, are obtained when substitutedphenylmalonic acids of the formula (XXXI)

 in which

X and Z are each as defined above, are reacted with acid halides, forexample thionyl chloride, phosphorus(V) chloride, phosphorus(III)chloride, oxalyl chloride, phosgene or thionyl bromide, if appropriatein the presence of catalysts, for example diethylformamide,methylstearylformamide or triphenylphosphine and, if appropriate, in thepresence of bases, for example pyridine or triethylamine, at atemperature between −20° C. and 200° C., preferably between 0° C. and150° C.

The substituted phenylmalonic acids of the formula (XXXI) in which Zdoes not represent hydrogen are novel. However, they may be prepared ina simple manner by known processes (cf., for example, Organikum, VEBDeutscher Verlag der Wissenschaften, Berlin 1977, p. 517 ff), forexample by hydrolysis of substituted phenylmalonic esters of the formula(XXXII)

in which

X, Z and R⁸ are each as defined above.

The carbonyl compounds of the formula (V) or their silyl enole ethers ofthe formula (Va)

in which

A, D and R⁸ are each as defined above, required as starting materialsfor process (D) according to the invention are compounds which arecommercially available, generally known or accessible by knownprocesses.

The malonic acid esters of the formula (XXXII)

in which

R⁸, X and Z are each as defined above, and Z is not hydrogen, are novel.

They can be prepared by generally known methods of organic chemistry(cf., for example, Tetrahedron Lett. 27, 2763 (1986) and Organikum VEBDeutscher Verlag der Wissenschaften, Berlin 1977, p. 587 ff).

The acid halides of the formula (VII), carboxylic anhydrides of theformula (VIII), chloroformic acid esters or chloroformic acid thioestersof the formula (IX), chloromonothioformic acid esters orchlorodithioformic acid esters of the formula (X), sulphonyl chloridesof the formula (XII), phosphorus compounds of the formula (XIII) andmetal hydroxides, metal alkoxides or amines of the formula (XIV) and(XV) and isocyanates of the formula (XVI) and carbamoyl chlorides of theformula (XVII) additionally required as starting materials for carryingout processes (F), (G), (H), (I), (J) and (K) according to the inventionare generally known compounds of organic or inorganic chemistry.

The compounds of the formulae (V), (VII) to (XVII), (XVIII), (XXI),(XXII), (XXIX), (XXX) and (XXXI) are moreover disclosed in the patentapplications cited at the outset and/or can be prepared by the methodsgiven there.

Process (A) is characterized in that compounds of the formula (II) inwhich A, B, X, Z and R⁸ are each as defined above are subjected to anintramolecular condensation in the presence of a diluent and in thepresence of a base.

Suitable diluents for the process (A) according to the invention are allorganic solvents which are inert to the reaction participants. Thosepreferably utilizable are hydrocarbons, such as toluene and xylene,furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, additionally polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethyl-formamideand n-methyl-pyrrolidone, and also alcohols such as methanol, ethanol,propanol, iso-propanol, butanol, iso-butanol and tert-butanol.

Suitable bases (deprotonating agents) for carrying out process (A)according to the invention are all customary proton acceptors. Thosepreferably utilizable are alkali metal and alkaline earth metal oxides,hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, each of which can also be employed inthe presence of a phase-transfer catalyst, for exampletriethylbenzylammonium chloride, tetrabutylammonium bromide, Adogene 464(=methyltrialkyl(C₈-C₁₀)ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine. Alkali metals such as sodium orpotassium can also be used. Furthermore, alkali metal and alkaline earthmetal amides and hydrides, such as sodium amide, sodium hydride andcalcium hydride, and additionally also alkali metal alkoxides, such assodium methoxide, sodium ethoxide and potassium tert-butoxide can beemployed.

When carrying out process (A) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (A) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (A) according to the invention, the reactioncomponent of the formula (II) and the deprotonating base are generallyemployed in equimolar to approximately double equimolar amounts.However, it is also possible to use one component or the other in arelatively large excess (up to 3 mol).

Process (B) is characterized in that compounds of the formula (III) inwhich A, B, X, Z and R⁸ are each as defined above are condensedintramolecularly in the presence of a diluent and in the presence of abase.

Suitable diluents for the process (B) according to the invention are allorganic solvents which are inert to the reaction participants. Thosepreferably utilizable are hydrocarbons, such as toluene and xylene,furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane,glycol dimethyl ether and diglycol dimethyl ether, and additionallypolar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methyl-pyrrolidone. Alcohols such as methanol,ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanolcan also be used.

Suitable bases (deprotonating agents) for carrying out the process (B)according to the invention are all customary proton acceptors. Thosepreferably utilizable are alkali metal and alkaline earth metal oxides,hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, each of which can also be employed inthe presence of phase-transfer catalysts, for exampletriethylbenzylammonium chloride, tetrabutylammonium bromide, Adogene 464(=methyltrialkyl(C₈-C₁₀-ammonium chloride) or TDA 1(=tris-(methoxyethoxyethyl)-amine). Alkali metals such as sodium orpotassium can also be used. Suitable are also alkali metal and alkalineearth metal amides and hydrides, such as sodium amide, sodium hydrideand calcium hydride, and also alkali metal alkoxides, such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide.

When carrying out process (B) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (B) according to the invention is generally carried out underatmospheric pressure.

When carrying out the process (B) according to the invention, thereaction components of the formula (III) and the deprotonating bases aregenerally employed in approximately equimolar amounts. However, it isalso possible to use one component or the other in a relatively largeexcess (up to 3 mol).

Process (C) is characterized in that compounds of the formula (IV) inwhich A, B, W, X, Z and R⁸ are each as defined above are cyclizedintramolecularly in the presence of an acid and, if appropriate, in thepresence of a diluent.

Suitable diluents for the process (C) according to the invention are allorganic solvents which are inert to the reaction participants. Thosepreferably utilizable are hydrocarbons, such as toluene and xylene,furthermore halogenated hydrocarbons, such as dichloromethane,chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, andadditionally polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methyl-pyrrolidone. Alcohols such as methanol,ethanol, propanol, iso-propanol, butanol, iso-butanol and tert-butanolcan also be used.

The acid employed can, if appropriate, also be used as a diluent.

Acids which can be employed in process (C) according to the inventionare all customary inorganic and organic acids, for example hydrohalicacids, sulphuric acid, alkyl-, aryl- and haloalkyl sulphonic acids;halogenated alkylcarboxylic acids, for example trifluoroacetic acid, areused in particular.

When carrying out process (C) according to the invention, the reactiontemperature can be varied within a relatively wide range. In general,the reaction is carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (C) according to the invention is generally carried out underatmospheric pressure.

When carrying out process (C) according to the invention, the reactioncomponents of the formulae (IV) and the acid are employed, for example,in equimolar amounts. However, it is, if appropriate, also possible toemploy the acid in catalytic amounts.

Process (D) according to the invention is characterized in that carbonylcompounds of the formula (V) or their silyl enol ethers of the formula(Va) are reacted with ketene acid halides of the formula (VI), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor.

Suitable diluents for the process (D) according to the invention are allorganic solvents which are inert to the reaction participants. Thosepreferably utilizable are hydrocarbons, such as o-dichlorobenzene,tetraline, toluene and xylene, furthermore ethers, such as dibutylether, glycol dimethyl ether and diglycol dimethyl ether, andadditionally polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide or N-methyl-pyrrolidone.

Acid acceptors which can be used when carrying out process (D) accordingto the invention are all customary acid acceptors.

Those preferably utilizable are tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hünig base or N,N-dimethyl-aniline.

When carrying out process (D) according to the invention, the reactiontemperature can be varied within a relatively wide range. The reactionis expediently carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 220° C.

Process (D) according to the invention is preferably carried out underatmospheric pressure.

When carrying out process (D) according to the invention, the reactioncomponents of the formulae (V) and (VI) and, if appropriate, the acidacceptor are in general employed in approximately equimolar amounts.However, it is also possbile to use one component or the other in arelatively large excess (up to 5 mol).

Process (Eα) is characterized in that compounds of the formulae (I-1-a)to (I-4-a) are in each case reacted with carboxylic acid halides of theformula (VII), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent.

Suitable diluents for the process (Eα) according to the invention areall solvents inert to the acid halides. Those preferably utilizable arehydrocarbons, such as benzine, benzene, toluene, xylene and tetraline,furthermore halogenated hydrocarbons, such as methylene chloride,chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene,and also ketones, such as acetone and methyl isopropyl ketone,furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxan,moreover carboxylic acid esters, such as ethyl acetate, and alsostrongly polar solvents, such as dimethylformamide, dimethylsulphoxideand sulpholane. If the stability to hydrolysis of the acid halidepermits, the reaction can also be carried out in the presence of water.

Suitable acid-binding agents in the reaction of process (Eα) accordingto the invention are all customary acid acceptors. Those preferablyutilizable are tertiary amines, such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethyl-aniline,furthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, and also alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate and also alkali metal hydroxides such as sodium hydroxide andpotassium hydroxide.

The reaction temperature in the process (Eα) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

When carrying out process (Eα) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-4-a) and the carboxylic acidhalide of the formula (VII) are in general each used in approximatelyequivalent amounts. However, it is also possible to employ thecarboxylic acid halide in a relatively large excess (up to 5 mol).Work-up is carried out according to customary methods.

Process (Eβ) is characterized in that compounds of the formulae (I-1-a)to (I-4-a) are each reacted with carboxylic anhydrides of the formula(VIII), if appropriate in the presence of a diluent and if appopriate inthe presence of an acid-binding agent.

Preferred diluents for the process (Eβ) according to the invention arethose diluents which are also preferred when using acid halides.Otherwise, a carboxylic anhydride employed in excess may alsosimultaneously function as diluent.

Possible acid-binding agents added in process (Eβ) are preferably thoseacid-binding agents that are also preferred when using acid-halides.

The reaction temperature in the process (Eβ) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

When carrying out process (Eβ) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-4-a) and the carboxylicanhydride of the formula (VIII) are in general each used inapproximately equivalent amounts. However, it is also possible to employthe carboxylic anhydride in a relatively large excess (up to 5 mol).Work-up is carried out according to customary methods.

In general, a procedure is used in which diluent and excess carboxylicanhydride and the resulting carboxylic acid are removed by distillationor by washing with an organic solvent or with water.

Process (F) is characterized in that compounds of the formulae (I-1-a)to (I-4-a) are in each case reacted with chloroformic acid esters orchloroformic acid thioesters of the formula (IX), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

Suitable acid-binding agents for process (F) according to the inventionare all customary acid acceptors. Those preferably utilizable aretertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBA, Hünigbase and N,N-dimethylaniline, furthermore alkaline earth metal oxides,such as magnesium oxide and calcium oxide, additionally alkali metal andalkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate and also alkali metal hydroxides such assodium hydroxide and potassium hydroxide.

Suitable diluents for the process (F) according to the invention are allsolvents which are inert to the chloroformic acid esters or chloroformicacid thioesters. Those preferably utilizable are hydrocarbons, such asbenzine, benzene, toluene, xylene and tetraline, furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, additionallyketones, such as acetone and methyl isopropyl ketone, furthermoreethers, such as diethyl ether, tetrahydrofuran and dioxan, moreovercarboxylic acid esters, such as ethyl acetate, furthermore nitriles,such as acetonitrile, and also strongly polar solvents, such asdimethylformamide, dimethyl sulphoxide and sulpholane.

When carrying out process (F) according to the invention, the reactiontemperature can be varied within a relatively wide range. The reactiontemperature is generally between −20° C. and +100° C., preferablybetween 0° C. and 50° C.

Process (F) according to the invention is in general carried out underatmospheric pressure.

When carrying out process (F) according to the invention, the startingmaterials of the formulae (I-1-a) to (I-4-a) and the appropriatechloroformic acid ester or chloroformic acid thioester of the formula(IX) are in general each used in approximately equivalent amounts.However, it is also possible to employ one component or the other in arelatively large excess (up to 2 mol). Work-up is carried out accordingto customary methods. In general, a procedure is used in whichprecipitated salts are removed and the reaction mixture which remains isconcentrated by stripping off the diluent.

Process (G) according to the invention is characterized in thatcompounds of the formula (I-1-a) to (I-4-a) are in each case reactedwith compounds of the formula (X) in the presence of a diluent and, ifappropriate, in the presence of an acid-binding agent.

In preparation process (G), about 1 mol of chloromonothioformic acidester or chlorodithioformic acid ester of the formula (X) is reacted permol of a starting material of the formulae (I-1-a) to (I-4-a), at 0 to120° C., preferably at 20 to 60° C.

Diluents which may be added, if appropriate, are all inert polar organicsolvents, such as ethers, amides, sulphones, sulphoxides, and alsohalogenoalkanes.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-4-a) is prepared by addition of strong deprotonating agents, forexample sodium hydride or potassium tert-butoxide, the further additionof acid-binding agents can be dispensed with.

If acid-binding agents are used, customary inorganic or organic basesare suitable; sodium hydroxide, sodium carbonate, potassium carbonate,pyridine and triethylamine may be mentioned by way of example.

The reaction can be carried out at atmospheric pressure or at elevatedpressure; it is preferably carried out at atmospheric pressure. Work-uptakes place according to customary methods.

Process (H) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-4-a) are in each case reactedwith sulphonyl chlorides of the formula (XII), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (H), about 1 mol of sulphonyl chloride of theformula (XII) is reacted per mol of starting material of the formulae(I-1-a) to (I-4-a) at −20 to 150° C., preferably at 0 to 70° C.

Process (H) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert polar organic solvents, such as ethers,amides, ketones, carboxylic acid esters, nitriles, sulphones,sulphoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide and methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compounds (I-1-a)to (I-4-a) is prepared by addition of strong deprotonating agents (forexample sodium hydride or potassium tert-butoxide), the further additionof acid-binding agents can be dispensed with.

If acid-binding agents are employed, customary inorganic or organicbases are suitable; sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine and triethylamine may be mentioned by way ofexample.

The reaction can be carried out at atmospheric pressure or at elevatedpressure; it is preferably carried out at atmospheric pressure. Work-uptakes place according to customary methods.

The process (I) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-4-a) are in each case reactedwith phosphorus compounds of the formula (XIII), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (I), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (XIII) is reacted per 1 mol of thecompounds (I-1-a) to (I-4-a) at temperatures between −40° C. and 150°C., preferably between −10° C. and 110° C., to give compounds of theformulae (I-1-e) to (I-4-e).

The process (I) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert polar organic solvents, such as ethers,carboxylic acid esters, halogenated hydrocarbons, ketones, amides,nitriles, sulphones, sulphoxides, etc.

Acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide ormethylene chloride are preferably employed.

Acid-binding agents which may be added, if appropriate, are customaryinorganic or organic bases, such as hydroxides, carbonates or amines. Byway of example, sodium hydroxide, sodium carbonate, potassium carbonate,pyridine and triethylamine may be mentioned.

The reaction may be carried out at atmospheric pressure or at elevatedpressure; it is preferably carried out at atmospheric pressure. Work-uptakes place according to conventional methods of organic chemistry. Theend products are preferably purified by crystallization, chromatographicpurification or by so-called “incipient distillation”, i.e. removal ofthe volatile constituents in vacuo.

Process (J) is characterized in that compounds of the formulae (I-1-a)to (I-4-a) are in each case reacted with metal hydroxides or metalalkoxides of the formula (XIV) or amines of the formula (XV), ifappropriate in the presence of a diluent.

Preferred diluents for process (J) according to the invention are etherssuch as tetrahydrofuran, dioxan and diethyl ether or else alcohols suchas methanol, ethanol and isopropanol, but also water. Process (J)according to the invention is generally carried out under atmosphericpressure. The reaction temperature is in general between −20° C. and100° C., preferably between 0° C. and 50° C.

Process (K) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-4-a) are in each case reactedwith (Kα) compounds of the formula (XVI), if appropriate in the presenceof a diluent and if appropriate in the presence of a catalyst, or (Kβ)with compounds of the formula (XVII), if appropriate in the presence ofa diluent and if appropriate in the presence of an acid-binding agent.

In preparation process (Kα), about 1 mol of isocyanate of the formula(XVI) is reacted per mole of starting material of the formulae (I-1-a)to (I-4-a) at 0 to 100° C., preferably at 20 to 50° C.

Process (Kα) is preferably carried out in the presence of a diluent.

Suitable diluents are all inert organic solvents, such as aromatichydrocarbons, halogenated hydrocarbons, ethers, amides, nitrites,sulphones or sulphoxides.

Catalysts may, if desired, be added to accelerate the reaction. Thecatalysts employed can very advantageously be organotin compounds, forexample dibutyltin dilaurate.

The reaction is preferably carried out at atmospheric pressure.

In preparation process (Kβ), about 1 mol of carbamoyl chloride of theformula (XVII) is reacted at 0 to 150° C., preferably at 20 to 70° C.,per mole of starting material of the formulae (I-1-a) to (I-4-a).

Possible diluents optionally added are all inert polar organic solvents,such as ethers, carboxylic acid esters, nitriles, ketones, amides,sulphones, sulphoxides or halogenated hydrocarbons.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If, in a preferred embodiment, the enolate salt of the compound (I-1-a)to (I-4-a) is prepared by addition of strong deprotonating agents (e.g.sodium hydride or potassium tertiary butoxide), the further addition ofacid-binding agents can be dispensed with.

If acid-binding agents are employed, customary inorganic or organicbases are suitable; those which may be mentioned by way of example aresodium hydroxide, sodium carbonate, potassium carbonate, triethylamineor pyridine.

The reaction can be carried out at atmospheric pressure or at elevatedpressure, preferably at atmospheric pressure. Work-up takes placeaccording to customary methods.

The active compounds are suitable for controlling animal pests,preferably arthropods and nematodes, in particular insects andarachnida, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

From the order of Isopoda, for example, Oniscus asellus, Armadillidiumvulgare and Porceillio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for exanple, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blatella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp, Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehnielia, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilusspp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallonsolstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention are distinguished by ahigh insecticidal and acaricidal activity.

They can be used to particularly good effect for controlling insectswhich are injurious to plants, such as, for example, against the larvaeof the mustard beetle (Phaedon cochleariae), against the larvae of thegreen rice leaf hopper (Nephotettix cincticeps) or against thecaterpillars of the cabbage moth (Plutella maculipennis) (cf. the UseExamples).

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes of methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates,alkylsulphates, arylsulphonates as well as albumen hydrolysis products;as dispersing agents there are suitable: for example lignin-sulphitewaste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas and substances produced by microorganisms.

Examples of particularly advantageous mixture components are thefollowing compounds:

Fungicides 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulphide, captafol, captan, carbendazim, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol,diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole,dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos,epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole,fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,fluoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole,furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole,hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodione, isoprothiolane, kasugamycin, copper preparations such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper,mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,methasulphocarb, methfuroxam, metiram, metsulphovax, myclobutanil,nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene(PCNB), sulphur and sulphur preparations, tebucanozole, tecloftalam,tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl,thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin. Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulphoton,edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH,heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazophos, isofenphos, isoprocarb, isoxathion, ivemectin,lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos,mesulphenphos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M,oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, RH 5992,salithion, sebufos, silafluofen, sulphotep, sulprofos, tebufenozid,tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos,terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,thiomethon, thionazin, thuringiensin, tralomethrin, triarathen,triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides

for example anilides such as, for example, diflufenican and propanil;arylcarboxylic acids such as, for example, dichloropicolinic acid,dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4-D,2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones such as, for example, chloridazon andnorflurazon; carbamates such as, for example, chlorpropham, desmedipham,phenmedipham and propham; chloroacetanilides such as, for example,alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlorand propachlor; dinitroanilines such as, for example, oryzalin,pendimethalin and trifluralin; diphenyl ethers such as, for example,acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen andoxyfluorfen; ureas such as, for example, chlortoluron, diuron,fluometuron, isoproturon, linuron and methabenz-thiazuron;hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim,sethoxydim and tralkoxydim; imidazolinones such as, for example,imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles such as,for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as,for example, mefenacet; sulphonylureas such as, for example,amidosulphuron, bensulphuron-methyl, chlorimuron-ethyl, chlorsulphuron,cinosulphuron, metsulphuron-methyl, nicosulphuron, primisulphuron,pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron andtribenuronmethyl; thiocarbamates such as, for example, butylate,cycloate, di-allate, EPTC, esprocarb, molinate, prosulphocarb,thiobencarb and tri-allate; triazines such as, for example, atrazine,cyanazine, simazine, simetryne, terbutryne and terbutylazine;triazinones such as, for example, hexazinone, metamitron and metribuzin;others such as, for example, aminotriazole, benfuresate, bentazone,cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr,ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben,pyridate, quinchlorac, quinmerac, sulphosate and tridiphane

The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use formsprepared from these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as ixodid ticks, argasid ticks, scab mites, trombiculid mites,flies (stinging and sucking), parasitic fly larvae, lice, hair lice,bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order Diptera and the sub-orders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.,

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Octodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

For example, they show an outstanding activity against Boophilusmicroplus and Lucilia cuprina.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which attack agriculturallivestock, such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese,honey bees, other domestic animals, such as, for example, dogs, cats,cage birds, aquarium fish, and so-called experimental animals such as,for example, hamsters, guinea-pigs, rats and mice. By controlling thesearthropods, it is intended to reduce mortality and decreased performance(in meat, milk, wool, hides, eggs, honey and the like), so that moreeconomical and simpler animal keeping is made possible by using theactive compounds according to the invention.

In the veterinary sector, the active compounds according to theinvention are used in a known manner by enteral administration, forexample in the form of tablets, capsules, drinks, drenches, granules,pastes, boluscs, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal application, by dermal administration, forexample in the form of dipping or bathing, spraying, pouring-on andspotting-on, washing, dusting, and with the aid of shaped articles whichcomprise active compound, such as collars, ear tags, tail marks, limbbands, halters, marking devices and the like.

When administered to livestock, poultry, domestic animals and the like,the active compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of 1 to 80% by weight, either directly or afterdilution by a factor of 100 to 10,000, or they may be used in the formof a chemical bath.

Furthermore, it has been found that the compounds of the formula (I)according to the invention have a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and as beingpreferred, but without any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Zyleborus spec., Tryptodendronspec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec., Dinoderus minutus.

Dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur.

Termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials are to be understood as meaning, in the presentcontext, non-live materials such as, preferably, synthetic materials,glues, sizes, paper and board, leather, wood and timber products, andpaint.

The materials to be very particularly protected against attack byinsects are wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention or mixtures comprising such a composition areto be understood as meaning, for example, construction timber, woodenbeams, railway sleepers, bridge components, jetties, wooden vehicles,boxes, pallets, containers, telephone poles, wood lagging, windows anddoors made of wood, plywood, particle board, joiner's articles, or woodproducts which, quite generally, are used in the construction of housesor in joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersant and/or binder or fixative, waterrepellent, if appropriate desiccants and UV stabilizers and, ifappropriate, colorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for the protection ofwood and wooden materials comprise the active compound according to theinvention at a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thespecies and the occurrence of the insects and on the medium. The optimumrate of application can be determined upon use in each case by testseries. However, in general, it suffices to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be protected.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-type organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

Organochemical solvents which are preferably employed are oily oroil-type solvents having an evaporation number of above 35 and aflashpoint of above 30° C., preferably above 45° C. Substances which areused as such oily and oil-type solvents which have low volatility andare insoluble in water are suitable mineral oils or their aromaticfractions, or mineral-oil-containing solvent mixtures, preferably whitespirit, petroleum and/or alkylbenzene.

Substances which are advantageously used are mineral oils with a boilingrange of 170 to 220° C., white spirit with a boiling range of 170 to220° C., spindle oil with a boiling range of 250 to 350° C., petroleumor aromatics of boiling range 160 to 280° C., essence of turpentine andthe like.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons ith a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-type solvents of low volatility having anevaporation number of above 35 and a flashpoint of above 30° C.,preferably above 45° C., can be partially replaced by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flashpoint ofabove 30° C., preferably above 45° C., and that theinsecticide/fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, part of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Substances which are preferably used are aliphaticorganochemical solvents having hydroxyl and/or ester and/or ethergroups, such as, for example, glycol ether, esters and the like.

The organochemical binders used within the scope of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and can be diluted with water and/or are soluble ordispersible or emulsifiable in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin, such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Up to 10% by weight of bitumen orbituminous substances can also be used as binders. In addition,colorants, pigments, water repellents, odour-masking substances andinhibitors or anticorrosives known per se and the like can also beemployed.

The composition or the concentrate preferably comprises, in accordancewith the invention, at least one alkyd resin or modified alkyd resinand/or a drying vegetable oil as the organochemical binder. Preferablyused according to the invention are alkyd resins with an oil content ofover 45% by weight, preferably 50 to 68% by weight.

All or some of the abovementioned binder can be replaced by a fixative(mixture) or a plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate,the phosphoric esters, such as tributyl phosphate, the adipic esters,such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearateor amyl stearate, the oleates, such as butyl oleate, the glycerol ethersor relatively high-molecular-weight glycol ethers, glycerol esters andp-toluene-sulphonic esters.

Fixatives are chemically based on polyvinyl alkyl ethers, such as, forexample, polyvinyl methyl ether, or ketones, such as benzophenone orethylene benzophenone.

Particularly suitable as a solvent or diluent is also water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective protection of wood is achieved by large-scaleindustrial impregnation processes, for example vacuum, double-vacuum orpressure processes.

If appropriate, the ready-to-use compositions can additionally compriseone or more other insecticides and, if appropriate, additionally one ormore fungicides.

Suitable additional components which may be admixed are, preferably, theinsecticides and fungicides mentioned in WO 94/29 268. The compoundsmentioned in that document are expressly part of the presentapplication.

Very particularly preferred components which may be admixed areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichloro-fluanide, tolylfluanide,3-iodo-2-propinylbutyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the examples below.

PREPARATION EXAMPLES Example (I-1-a-1)

At 80° C., 17.9 g of the compound of Example II-1 in 36 ml of anhydrousdimethylformamide (DMF) are added dropwise to 14.94 g (0.128 mol) ofpotassium tert-butoxide in 51 ml of anhydrous DMF, and the mixture isstirred at room temperature for 1.5 hours. 440 ml of ice-water are thenadded and the mixture is acidified to pH 1 at 0-20° C. usingconcentrated HCl and the precipitate is filtered off with suction anddried. The crude product is stirred with methyl tert-butyl ether(MTBE)/n-hexane, filtered off with suction and dried.

Yield: 10 g (62% of theory); mp.: >220° C.

Similar to Example (I-1-a-1) and/or according to the general preparationinstructions, the following compounds of the formula (I-1-a) areobtained:

(I-1-a)

Ex. mp. No. X Z A B Isomer ° C. I-1-a-2 CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂—β >220 I-1-a-3 CH₃ CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— β >220 I-1-a-4 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-5 OCH₃ H —(CH₂)₂—CHCH₃—(CH₂)₂— β 181 I-1-a-6 i-C₃H₇ H —(CH₂)₂—CHCH₃—(CH₂)₂— β  193 I-1-a-7 Cl NO₂—(CH₂)₂—CHCH₃—(CH₂)₂— β >220 I-1-a-8 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— β 128 I-1-a-9 OCH₂—C₆H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂— β  188 I-1-a-10 CH₃ CH₃i-C₃H₇ CH₃ —  117 I-1-a-11 CH₃ CH₃ CH₃ CH₃ —  210 I-1-a-12 Br OCH₃—(CH₂)₂—CHCH₃—(CH₂)₂— β >220 I-1-a-13 Cl NH₂ —(CH₂)₂—CHCH₃—(CH₂)₂— βI-1-a-14 OCH₃ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-15 Br OCH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-16 Cl CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂—β >220 I-1-a-17 F OCH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-18 CH₃ CH₃—(CH₂)₂—O—(CH₂)₂— —  215 I-1-a-19 Cl Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— β  218I-1-a-20 F F —(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-21 Br Br—(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-22 Cl H —(CH₂)₂—CHOCH₃—(CH₂)₂— β 218 I-1-a-23 Cl NO₂ —(CH₂)₂—CHOCH₃—(CH₂)₂— β >220 I-1-a-24 F CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— β 200-201

Example (I-1-b-1)

2.3 g (8 mmol) of the compound of Example I-1-a-2 are precharged in 50ml of anhydrous ethyl acetate and admixed with 1.34 ml (9.6 mmol) oftriethylamine, and 1.01 ml (9.6 mmol) of isobutyryl chloride in 5 ml ofanhydrous ethyl acetate are added dropwise under reflux. After 16 hoursat reflux, the mixture is concentrated and the residue is taken up inmethylene chloride, washed 2× with 50 ml of 0.5N NaOH each time, driedand evaporated. The residue is recrystallized from methyl tert-butylether (MTB ether)/n-hexane.

Yield: 1.8 g (Δ 62% of theory) mp.: 163° C.

Similar to Example (I-1-b-1) and/or according to the general preparationinstructions, the following compounds of the formula (I-b-1) areobtained:

(I-1-b)

mp. Ex. No. X Z A B R¹ ° C. Isomer I-1-b-2 i-C₃H₇ H—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇— 183 β I-1-b-3 i-C₃H₇ H—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉— 198 β I-1-b-4 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇— 170 β I-1-b-5 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉—CH₂— 198 β I-1-b-6 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— 4-Cl—C₆H₄— 213 β I-1-b-7 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 145 β I-1-b-8 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉—CH₂— 194 β I-1-b-9 CH₃ CH₃ CH₃ CH₃ i-C₃H₇—188 — I-1-b-10 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— i-C₃H₇— 143 β I-1-b-11 BrOCH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇— 151 β I-1-b-12 Cl NO₂—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇— >220  β I-1-b-13 O—CH₂—C₆H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇— 161 β I-1-b-14 CH₃ CH₃ i-C₃H₇ CH₃C₂H₅—O—CH₂— 103 — I-1-b-15 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₄H₉— 157 βI-1-b-16 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— cyclohexyl 171 β I-1-b-17 CH₃CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅O—CH₂— 131 β I-1-b-18 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— 4-Cl—C₆H₄— 164 β I-1-b-19 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂—

164 β I-1-b-20 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 129 β I-1-b-21OCH₃ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 216-218 β I-1-b-22 Br OCH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 123-124 β I-1-b-23 Cl CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— β I-1-b-24 Br Br —(CH₂)₂—CHOCH₃—(CH₂)₂—i-C₃H₇— 199-200 β I-1-b-25 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃— 187-188β I-1-b-26 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— i-C₄H₉— 110-111 β I-1-b-27CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— C₂H₅O—CH₂— β I-1-b-28 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— cyclohexyl 162-164 β I-1-b-29 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— 4-Cl—C₆H₄— >225 β I-1-b-30 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂—

181 β I-1-b-31 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— s-C₄H₉— 103-104 β

Example I-1-c-1

2.3 g (8 mmol) of the compound of Example I-1-a-2 are precharged in 50ml of anhydrous methylene chloride and admixed with 1.12 ml (8 mmol) oftriethylamine, and 0.8 ml (8 mmol) of ethyl chloroformate in 5 ml ofanhydrous methylene chloride are added dropwise at 0-10° C. Stirring iscontinued at room temperature and the reaction is monitored by TLC. Themixture is then washed 2× with 50 ml of 0.5N NaOH each time, dried andevaporated, and the residue is recrystallized from MTB ether/n-hexane.

Yield: 1.7 g (Δ 59% of theory) mp.: 135° C.

Similar to Example (I-1-c-1) and/or according to the general preparationinstructions, the following compounds of the formula (I-1-c) areobtained:

(I-1-c)

mp. Ex. No. X Z A B M R² ° C. Isomer I-1-c-2 i-C₃H₇ H—(CH₂)₂—CHCH₃—(CH₂)₂— O C₂H₅ 198 β I-1-c-3 CH₃ CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—O C₂H₅ 146 β I-1-c-4 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 128 β I-1-c-5CH₃ CH₃ CH₃ CH₃ O C₂H₅ 139 — I-1-c-6 CH₃ CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— OC₂H₅ 126 β I-1-c-7 Br OCH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— O C₂H₅ 175 β I-1-c-8 ClNO₂ —(CH₂)₂—CHCH₃—(CH₂)₂— O C₂H₅ 236 β I-1-c-9 O—CH₂—C₆H₅ H—(CH₂)₂—CHCH₃—(CH₂)₂— O C₂H₅ 131 β I-1-c-10 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O i-C₄H₉— 122 β I-1-c-11 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₆H₅—CH₂ 139 β I-1-c-12 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₆H₅— 193 β I-1-c-13 OCH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅— 208-211 β I-1-c-14 Br OCH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅— 180-182 β I-1-c-15 Cl CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅— 153-155 β I-1-c-16 Br Br—(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅— >230  β I-1-c-17 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— O i-C₄H₉— 137-139 β I-1-c-18 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— O C₆H₅—CH₂ 135-137 β I-1-c-19 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— S i-C₃H₇— 152-154 β I-1-c-20 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— S t-C₄H₉— 200-201 β I-1-c-21 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— S C₆H₅—CH₂— 148-149 β

Example I-1-g-1

1.8 g (6 mmol) of the compound of Example I-1-a-4 and 1.2 ml (1.5 eq)triethylamine are precharged in 50 ml of methyl acetate and heated underreflux. 0.91 ml (1.1 g; 1.3 eq) of morpholine-N-carboxylic acid chloridein 5 ml of methyl acetate are added. The mixture is heated under refluxover night, concentrated and the residue is taken up in CH₂Cl₂. Theorganic phase is washed twice with 40 ml of N NaOH each time, dried andconcentrated. The residue (2.7 g) is stirred with petrol ether, filteredoff with suction and dried. Yield: 0.90 g (36% of theory), mp.: 132° C.

Example I-1-g-2

Similar to Example I1-g-1 and/or according to the general preparationinstructions the compound is obtained as an oil:

Example (II-1)

At 0-10° C., 16.9 g of 2-methylphenylacetyl chloride in 20 ml ofanhydrous tetrahydrofuran (THF) are added dropwise to 20.8 g of methyl1-amino-4-methylcyclohexanecarboxylate and 29.4 ml (0.21 mol) oftriethylamine in 200 ml of anhydrous THF, and the mixture is stirred atroom temperature. After the reaction has ended (control by thin-layerchromatography (TLC)), the mixture is concentrated, taken up in amixture of 0.5N HCl/methylene chloride and the organic phase is driedand concentrated. The residue is recrystallized from MTBE/n-hexane.

Yield: 17.9 g (59% of theory); mp.: 107° C.

Similar to Example (II-1) and/or according to the general preparationinstructions, the following compounds of the formula (II) are obtained:

(II)

mp. Ex. No. X Z A B R⁸ Isomer ° C. II-2 CH₃ H —CH₂)₂—CHOCH₃—(CH₂)₂— CH₃β  98 II-3 CH₃ CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ β 120 II-4 CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β  90 II-5 CH₃ CH₃ CH₃ CH₃ CH₃ — II-6 OCH₃ H—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ β 138 II-7 O—CH₂—C₆H₅ H —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ β  85 II-8 OCH₃ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 149 II-9 CH₃ CH₃—(CH₂)₂—CHOC₂H₅—(CH₂)₂— CH₃ β 108 II-10 CH₃ CH₃ i-C₃H₇ CH₃ CH₃ —  75II-11 CH₃ CH₃ —(CH₂)₂—O—(CH₂)₂— CH₃ — 153 II-12 Cl NO₂—CH₂)₂—CHCH₃—(CH₂)₂— CH₃ β 158 II-13 Cl Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β112 II-14 Cl CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 171 II-15 Cl H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β  68 II-16 Br OCH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃β 131 II-17 Br OCH₃ —CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 158 II-18 Br Br—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 132 II-19 F CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃β 74-76 II-20 F OCH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 169 II-21 F F—(CH₂)₂—CHOCH₃—(CH₃)₂— CH₃ β  91 II-22 Cl NH₂ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃β  94 II-23 Cl NO₂ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 127 II-24 Cl Br—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 126-128 II-25 Cl CF₃ —(CH₂)₂—CHOCH₃—(CH₂)₂—CH₃ β 109-111 II-26 Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ β 100-102

Example (II-10)

At an internal temperature of 30 to 40° C., 16.7 g of the compound ofExample (XXVIII-1) in 200 ml of methylene chloride are added dropwise to32.2 g (0.326 mol) of concentrated sulphuric acid, and the mixture isstirred for a further 2 hours at this temperature. 42 ml of anhydrousmethanol are then added dropwise in such a way that an internaltemperature of 40° C. is obtained. The mixture is stirred at 40 to 70°C. for a further 6 hours, poured onto 0.35 kg of ice and extracted withmethylene chloride, the organic phase is washed with aqueous NaHCO₃solution, dried and concentrated and the residue is crystallized fromMTBE/n-hexane.

Yield: 7.40 g (39% of theory), mp.: 75° C.

Example (II-22)

37 g of the compound of Example (II-12) in 370 ml of ethanol are admixedwith Raney nickel and hydrogenated. The catalyst is filtered off, thefiltrate is concentrated and the residue is recrystallized fromMTBE/n-hexane. 10.3 g of a solid of mp.: 94° C. are obtained.Concentration of the mother liquor affords a further 20 g of product asan oil.

Total yield: 89% of theory.

Example (I-2-a-1)

At 0 to 10° C., a solution of 16.6 g (50 mmol) of1-ethyloxycarbonyl-cyclohexyl 2-chlorophenylacetate according to Example(III-1) in 50 ml of tetrahydrofuran (THF) are added dropwise to 8.42 g(75 mmol) of potassium tert-butoxide in 50 ml of anhydrous THF, and themixture is stirred at room temperature for 16 h.

For work-up, the reaction mixture is added dropwise to 500 ml ofice-cold 1N HCl, and the precipitated product is filtered off withsuction, washed with water and dried in a vacuum drying cabinet.

Yield: 10.19 g (80% of theory) of mp.: 231° C.

Similar and/or according to the general preparation instructions, thefollowing compounds of the formula (I-2-a) are obtained:

(I-2-a)

mp. Ex. No. X Z A B ° C. I-2-a-2 CH₃ H —(CH₂)₅— 233 I-2-a-3 OCH₃ H—(CH₂)₅— 177 I-2-a-4 F H —(CH₂)₅— 233 I-2-a-5 i-C₃H₇ H —(CH₂)₅— 200I-2-a-6 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— 180 I-2-1-7 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— 240

Example (I-2-b-1)

2.79 g (10 mmol) of the compound of Example (I-2-a-1) are precharged in50 ml of anhydrous THF, 1.21 g (12 mmol) of triethylamine are added, asolution of 1.33 g (11 mmol) of pivaloyl chloride is added dropwise withice cooling, and the mixture is stirred at room temperature for 16 h.For work-up, the mixture is stirred into 200 ml of water and the productis filtered off with suction and dried.

Yield: 3.5 g (98% of theory) of mp.: 128° C.

Similar and/or according to the general preparation instructions, thefollowing compounds of the formula (I-2-b) are obtained:

(I-2-b)

mp. Ex. No. X Z A B R¹ ° C. I-2-b-2 CH₃ H —CH₂)₅— t-C₄H₉ 101 I-2-b-3 ClH —(CH₂)₅— H₅C₂—C(CH₃)₂— 90-92 I-2-b-4 OCH₃ H —(CH₂)₅— t-C₄H₉ oilI-2-b-5 F H —(CH₂)₅— t-C₄H₉ 88 I-2-b-6 i-C₃H₇ H —(CH₂)₅— t-C₄H₉ 98I-2-b-7 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 91 I-2-b-8 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 104-106

Example (I-2-c-1)

At 0 to 10° C., 1.43 g of the compound of Example (I-2-a-7) in 30 ml ofmethylene chloride are admixed with 0.55 g of triethylamine and 0.75 gof isobutyl chloroformate.

Work-up is carried out as described in Example (I-1-c-1).

Yield: 0.94 g; m.p.: 70° C.

Example (I-2-c-2)

This compound was obtained in a similar manner starting from thecompound of Example (I-2-a-6).

Yield: 1.7 g, semicrystalline.

Example (III-1)

8.6 g (50 mmol) of 2-chlorophenylacetyl chloride together with 8.6 g (50mmol) of ethyl 1-hydroxy-cyclohexanecarboxylate are stirred for 5 hoursat 120° C. and degassed using an oil pump.

Yield: 15.26 g of 1-ethoxycarbonyl-cyclohexyl 2-chlorophenylacetate as acolourless oil.

¹H NMR (300 MHz, CDCl₃): δ=1.18 (t, 3H, CH₂ CH ₃), 1.2-1.82 (m, 8H,c-Hcx), 2.12 (m, 2H, c-Hcx), 3.81 (s, 2H, CH ₂—CO), 4.14 (q, 2H, O—CH₂—CH₃), 7.15-7.4 (m, 4H, Ar-H)

In a similar manner and/or according to the general preparationinstructions, the following compounds of the formula (III) are obtained:

(III)

Ex. mp. No. X Z A B R⁸ ° C. III-2 CH₃ H —(CH₂)₅— C₂H₅ oil III-3 OCH₃ H—(CH₂)₅— C₂H₅ oil III-4 F H —(CH₂)₅— C₂H₅ oil III-5 i-C₃H₇ H —(CH₂)₅—C₂H₅ oil III-6 CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅ oil III-7 CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— C₂H₅ oil

Example (I-3-a-1)

19 g of the compound of Example (IV-1) in 86 ml of toluene and 43 ml oftrifluoroacetic acid are heated under reflux overnight. Excesstrifluoroacetic acid is removed under reduced pressure, the residue istaken up in 400 ml of water and 120 ml of MTBE and the pH is adjusted toa value of 14 by adding NaOH. The mixture is extracted twice with MTBEand the aqueous phase is acidified with HCl and extracted 3 times withMTBE. The organic phase is dried and evaporated.

Yield: 7.8 g (63% of theory); m.p.: 185-187° C.

Example (I-3-b-1)

1.5 g of the compound of Example (I-3-a-1) in 20 ml of methylenechloride are admixed with 1.08 ml of triethylamine. Cooling with ice, asolution of 0.96 ml of pivaloyl chloride in 3 ml of methylene chlorideis added dropwise, and stirring is continued at room temperature for afurther 2 hours. The mixture is washed twice with 10% strength citricacid and extracted with methylene chloride. The combined organic phasesare washed twice with 1N NaOH, and the aqueous alkaline phases areextracted with methylene chloride. The combined organic phases are driedand concentrated.

Yield: 1.90 g (98% of theory); m.p.: 79-83° C.

Example (I-3-b-2)

Similar to Example (I-3-b-1), when using isobutyryl chloride instead ofpivaloyl chloride the following compound of m.p.: 149-152° C. isobtained in quantitative yield:

Example (I-3-c-1)

Similar to Example (I-3-b-1), when using isobutyl chloroformate insteadof pivaloyl chloride the following compound of m.p.: 101-103° C. isobtained in a yield of 98% of theory:

Example (IV-1)

A: 10 g of the compound (1) in 40 ml of toluene are admixed with 1 dropof DMF and 6.4 g of thionyl chloride and stirred for 5 minutes at roomtemperature and then at 100° C. until the formation of gas ceases.Excess thionyl chloride is removed (high vacuum) and the acid chlorideis dissolved in 20 ml of THF (tetrahydrofuran): Solution A.

B: At 0° C., 10.7 g of the compound (2) in 20 ml of THF are addeddropwise to 32 ml of a solution of lithium diisopropylamide (LDA) (65.8mmol) in 50 ml of THF, and the mixture is stirred at 0° C. for 30minutes. The solution A is then added dropwise at this temperature, andthe mixture is stirred for a further 1 hour without cooling.

The mixture is admixed with 175 ml of MTBE and a few drops of water. Themixture is then washed twice with 10% strength aqueous ammonium chloridesolution and the organic phase is dried and concentrated. Yield: 19 g(oil).

¹H NMR (400 MHz, CDCl₃): 1.2-2.0 (m, 10H, CH₂); 2.32, 2.38 (2s, 2×3H;CH₃), 3.22 (dd, 2H, CH₂); 3.71, 3.76 (2s, 2×3H, OCH₃); 6.7-7.4 (M, 7H,Phenyl-H).

Example (I-4-a-1)

1.9 g (10 mmol) of 2-(2-methyl-phenyl)-chlorocarbonylketene wereprecharged in 20 ml of anhydrous toluene. After the addition of 1.4 g(10 mmol) of ethyl 2-pyridyl ketone, the mixture is heated under refluxfor 8 h. After cooling, the precipitate is filtered off with suction andwashed twice with cyclohexane.

Yield: 2.1 g (71% of theory); m.p.: 105-107° C.

In a similar manner and/or according to the general preparationinstructions, the following compounds of the formula (I-4-a) areobtained:

(I-4-a)

Ex. No. X Z A D mp. ° C. I-4-a-2 CH₃ H CH₃ 4-F-Phenyl 187-190 I-4-a-3 ClH CH₃ CH₃  97-100 I-4-a-4 Cl H —[C(CH₃)₂]—O—[C(CH₃)₂]— 194-196 I-4-a-5CH₃ CH₃ —[C(CH₃)₂]—O—[C(CH₃)₂]— 174-175 I-4-a-6 CH₃ CH₃ —(CH₂)₄— 198-200I-4-a-7 CH₃ CH₃ CH₃ 2-Pyridyl  99-102 I-4-a-8 CH₃ CH₃ CH₃ 4-Pyridyl273-275 I-4-a-9 CH₃ CH₃ CH₃ CH₃ 57-59

Example (I-4-b-1)

1.2 g (4 mmol) of the compound of Example (I-4-a-7) in 10 ml of ethylacetate are admixed with 0.4 g (4 mmol) of triethylamine, and at 0° C.0.7 g (4 mmol) of 6-chloropyrid-3-yl-carbonyl chloride dissolved in 4 mlof ethyl acetate are added dropwise. The mixture is kept for 20 hours atroom temperature and the precipitate is filtered off with suction andwashed with ethyl acetate. The organic phase is washed twice with 20 mlof half concentrated aqueous NaCl solution each time, dried andconcentrated.

Yield: 2 g (91% of theory), m.p.: 70 to 73° C.

Similar to Example (I-4-b-1) and/or according to the general preparationinstructions, the following compounds of the formula (I-4-b) areobtained:

(I-4-b)

mp. Ex. No. X Z A D R¹ ° C. I-4-b-2 CH₃ CH₃ CH₃ 2-Pyridyl 4-Cl-Phenyl73- 75 I-4-b-3 CH₃ CH₃ CH₃ 2-Pyridyl CH₃ 119- 120 I-4-b-4 CH₃ CH₃ CH₃2-Pyridyl

120- 121 I-4-b-5 CH₃ CH₃ CH₃ 2-Pyridyl

119- 121 I-4-b-6 CH₃ CH₃ CH₃ 2-Pyridyl

120- 122

Example (I-4-c-1)

1.5 g (5 mmol) of the compound of Example (I-4-a-7) in 20 ml of ethylacetate are admixed with 0.5 g (5 mmol) of triethylamine, and at 0° C.0.47 g (5 mmol) of methyl chloroformate in 5 ml of ethyl acetate areadded dropwise. The mixture is stirred for 20 hours at room temperatureand the precipitate is separated off and washed with ethyl acetate. Theorganic phase is washed twice with 25 ml of half concentrated aqueousNaCl solution each time, dried and concentrated.

Yield: 1.7 g (93% of theory); m.p.: 136-137° C.

Example (XXXII-1)

236 g (2.8 mol) of dimethyl carbonate are precharged in 814 ml ofanhydrous toluene, and 27.3 g (0.91 mol) of sodium hydride (80%) areadded. At 80° C., 133 g (0.7 mol) of methyl 2-chlorophenylacetate areadded dropwise, and the mixture is stirred at 80-90° C. for 16 h. Themixture is poured into 2 l of ice water and acidified withhalf-concentrated HCl to pH 4, the organic phase is separated off andthe aqueous phase is extracted with 150 ml of toluene. The combinedorganic phases are dried, the solvent is distilled off and the residueis distilled using high vacuum.

Yield: 122.9 g (72% of theory) bp_(0.6-0.7 mbar) 129-131° C.

In a similar manner and/or according to the general preparationinstructions, the following compounds of the formula (XXXII) areobtained:

(XXXII)

Ex. No. X Z R⁸ bp. XXXII-2 CH₃ H CH₃ used as crude product XXXII-3 CH₃CH₃ CH₃ ¹H NMR(400 MHz, CDCl₃): δ=2.25(s, 3H, CH₃); 1.28(3H, s, CH₃);3.78(s, 6-H, 2 x CO₂CH₃); 4.88(s, 1H, CH).

Example (XXXI-1)

93.3 g (1.67 mol) of potassium hydroxide are dissolved in 125 ml ofwater and admixed with 250 ml of methanol. 121.3 g (0.5 mol) of thecompound of Example (XXXII-1) are then added dropwise. After 5 h atreflux, the mixture is evaporated and the residue is dissolved in ethylacetate and, at 0° C., carefully acidified with concentratedhydrochloric acid. The precipitate is filtered off with suction anddried over calcium chloride under reduced pressure.

Yield: 29.2 g (27% of theory); m.p.: 135-136° C. (decomposition).

In a similar manner and/or according to the general preparationinstructions, the following compounds of the formula (XXXI) areobtained:

(XXXI)

Ex. No. X Z mp. ° C. XXXI-2 CH₃ H 149-150 (Decomp.) XXXI-3 CH₃ CH₃ 150

Example (VI-1)

27.9 g (0.13 mol) of 2-(2-chloro-phenyl)-malonic acid are precharged in32 ml of anhydrous toluene, 59 g (0.391 mol) of thionyl chloride areadded dropwise and the mixture is heated under reflux for 5 hours. Afterconcentration and distillation, 20.7 g (74% of theory) of2-(2-chlorophenyl)-2-chlorocarbonylketene of bp._(1 mbar) 102° C. areobtained.

In a similar manner and/or according to the general preparationinstructions, the following compounds of the formula (VI) are obtained:

(VI)

Ex. No. X Y bp. ° C. VI-2 CH₃ H 92-94 (0.6 mbar) VI-3 CH₃ CH₃ ¹H NMR(400MHz, CDCl₃) δ=2.20, 2.21(2s, 6H, 2CH₃); 7.05(m, 3H, Ph—H).

Example (XXII-1)

A solution of 5.10 g of 98% strength lithium hydroxide in 220 ml ofwater is added dropwise to 55 g of the carboxylic acid ester of Example(XXIII-1) shown above in 220 ml of THF, and the mixture is stirred atroom temperature overnight. The mixture is then evaporated, the residueis admixed with water and extracted with MTBE, the aqueous phase isacidified with concentrated hydrochloric acid and the precipitated acidis filtered off with suction.

Similar to Example (XXII-1) and/or according to the general preparationinstructions, the following compounds of the formula (XXII) areobtained:

(XXII)

Ex. No. X Z mp. ° C. XXII-2 OCH₃ Cl 128-130 XXII-3 Cl CH₃ 116-120 XXII-4F CH₃  89 XXII-5 Br Br  95 XXII-6 F F 118 XXII-7 Cl Br 115 XXII-8 Cl CF₃110 XXII-9 Br CH₃ 117

Example (XXIII-1)

With cooling, 1020 ml of a 30% strength aqueous NaOCH₃ solution (5.67mol) are added dropwise to 653 g (1.26 mol) (68% pure) of the compoundof Example (XXIV-1) in 220 ml of methanol, and the mixture is stirred atreflux for 5 hours. With cooling, 200 ml of concentrated sulphuric acidare then added dropwise, and the mixture is stirred under reflux for afurther 1 hour.

The mixture is concentrated, admixed with water and extracted withmethylene chloride. The extract is dried and concentrated.

Crude yield: 355 g (81% pure).

Similar to Example (XXIII-1) and/or according to the general preparationinstructions, the following compounds of the formula (XXIII) areobtained:

(XXIII)

Ex. No. X Z R⁸ bp_(mbar) ° C. XXIII-2 OCH₃ Cl CH₃ 120 0.09 XXII-3 Cl CH₃CH₃ 125 0.1 XXIII-4 F CH₃ CH₃ 60 0.05 XXIII-5 Br Br CH₃ GC/MS 308(M⁺,4%) 249(42%) 227(77%) XXIII-6 F F CH₃ 100 0.03 XXIII-7 Cl Br CH₃ 101°C./0.25 mbar XXIII-8 Cl CF₃ CH₃ Kp: 110° C./ 0.35 mbar XXIII-9 Br CH₃CH₃ GC/MS 183(29%) 163(100%)

Example (XXIV-1)

Under argon, 202.9 g of anhydrous copper(II) chloride and then 1890 g of1,1-dichloroethane are added to 229 g of isopentyl nitrite in 750 ml ofanhydrous acetonitrile. Below 30° C., 204 g of 2,5-dichloroaniline areadded a little at a time, and the mixture is stirred at room temperatureovernight until the formation of gas ceases. The mixture is poured into3600 ml of ice-cold 20% strength hydrochloric acid, stirred for 10minutes and extracted repeatedly with MTBE. The organic phase is washedwith 20% strength HCl, dried and concentrated.

MS in accordance with the structure.

Similar to example (XXIV-1) and/or according to the general preparationinstructions, the following compounds of the formula (XXIV) areobtained:

(XXIV)

Ex. No. X Z GC/MS XXIV-2 OCH₃ Cl 274(12%, M⁺) 155(100%) XXIV-3 Cl CH₃256(5%, M⁺) 185(7%) 139(100%) XXIV-4 F CH₃ 242(7%, M⁺) 123(100%) XXIV-5Br Br 366(13%, M⁺) 249(100%) XXIV-6 F F 246(5%, M⁺) 127(100%) XXIV-7 ClBr M⁺322(17%) 205(100%) XXIV-8 Cl CF₃ M⁺312(4%) 193(100%) XXIV-9 Br CH₃M⁺302(22%) 185(100%)

Example (XXVIII-1)

At 0 to 10° C., 14.9 g of 2,5-dimethylphenylacetyl chloride in 20 ml ofTHF are added dropwise to 9 g (0.08 mol) of the aminonitrile shown abovein 160 ml of THF and 12.3 ml of triethylamine.

After the reaction has ended, the mixture is concentrated, the residueis taken up in 0.5N HCl/methylene chloride and the organic phase isdried and concentrated. The residue is chromatographed over silica gelusing n-hexane/ethyl acetate.

Yield: 16.70 g (80% of theory); m.p.: 89° C.

Example (XXVIII-2)

In a similar manner, the compound of the formula

is obtained in quantitative yield: m.p.: 198° C.

Use Examples Example A

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae) while theleaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, for example the compounds of Preparation Examples(I-1-a-1) and (I-4-a-1) at an exemplary active compound concentration of0.1% caused a destruction of in each case 100% after 7 days.

Example B

Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis) while the leaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example the compounds of preparation examples(I-4-a-1) and (I-4-a-2) at an exemplary active compound concentration of0.1% caused a destruction of in each case 100% after 7 days.

Example C

Spodoptera Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with caterpillars of the owlet moth (Spodoptera frugiperda) aslong as the leaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example the compounds of preparation examples(I-1-a-1) and (I-4-a-1) at an exemplary active compound concentration of0.1% caused a destruction of in each case 85% after 7 days.

Example D

Myzus Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which have been heavily infested withthe peach aphid (Myzus persicae) are treated by being dipped into thepreparation of the active compound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the aphids have been killed; 0% means that none ofthe aphids have been killed.

In this test, for example the compounds of preparation examples(I-2-a-1), (I-2-b-1), (I-2-b-2), (I-1-a-1) and (I-4-a-1) at an exemplaryactive compound concentration of 0.1% caused a destruction of in eachcase at least 90% after 6 days.

Example E

Nephotettix Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryzae sativa) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with larvae of the green rice leaf hopper (Nephotettixcincticeps) while the seedlings are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the larvae have been killed; 0% means that none ofthe larvae have been killed.

In this test, for example the compounds of preparation examples(I-2-a-2), (I-2-b-3), (I-1-a-1), (I-4-a-1) and (I-4-a-2) at an exemplaryactive compound concentration of 0.1% caused a destruction of in eachcase 100% after 6 days.

Example F

Tetranychus Test (OP Resistant)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) heavily infested by all stages of thecommon spider mite (Tetranychus urticae) are dipped into a preparationof the active compound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, for example the compounds of preparation examples(I-2-a-1), (I-2-a-2), (I-2-b-1) and (I-2-b-2) at an exemplary activecompound concentration of 0.1% had an efficacy of in each case at least98% after 9 days.

Example G

Tetranychus Test (OP Resistant/Dip Treatment)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) heavily infested by all stages of thecommon spider mite (Tetranychus urticae) are dipped into a preparationof the active compound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, for example the compounds of preparation examples(I-2-a-1), (I-2-a-2), (I-2-b-1) and (I-2-b-2) at an exemplary activecompound concentration of 0.01% had an efficacy of in each case at least95% after 13 days.

Example H

Panonychus Test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Plum trees (Prunus domestica) approximately 30 cm in height which areseverely infested by all stages of the fruit tree spider mite(Panonychus ulmi) are sprayed with an active compound preparation of thedesired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed; 0% means thatnone of the spider mites have been killed.

In this test, for example the compounds of preparation examples(I-2-b-1) and (I-2-b-2) at an exemplary active compound concentration of0.004% had an efficacy of in each case 100% after 7 days.

Example I

Test With Fly Larvae/Development-inhibitory Action

Test animals:

All larval stages of Lucilia cuprina (OP resistant) [pupae and adults(without contact with the active compound)]

Solvent:

35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation, 3 parts by weight of active compoundare mixed with 7 parts of the abovementioned solvent-emulsifier mixture,and the resulting emulsion concentrate is diluted with water to thedesired concentration in each case.

For each individual concentration, 30 to 50 larvae are introduced into atest tube which contains 1 cm³ of horse meat. 500 μl of the dilution tobe tested are pipetted onto this horse meat. The test tubes are placedin plastic beakers whose bottom is covered with sea sand, and kept in aclimatized room (26° C. ±1.5° C., 70% ±10% relative humidity). Theactivity is examined (larvicidal action) after 24 hours and again after48 hours. After emergence of the larvae (about 72 h), the test tubes areremoved and perforated plastic lids are fitted to the beakers. After 1.5times the development time (hatching of the control flies), the hatchedflies and the pupae/coccoons are counted.

The activity criterion is the incidence of death in the treated larvaeafter 48 h (larvicidal effect), or the inhibition of the hatching ofadults from pupae or the inhibition of pupa formation. The criterion forthe in vitro activity of a substance is the inhibition of thedevelopment of the flies, or a development standstill before the adultstage. 100% larvicidal action means that all the larvae have been killedafter 48 hours. 100% development-inhibitory action means that no adultflies have hatched.

In this test, a development-inhibitory action of 100% was shown, forexample, by the compound of Preparation Example (I-2-b-3) at anexemplary active compound concentration of 1000 ppm.

Example K

Test With Boophilus Microplus Resistant/SP Resistant Parkhurst Strain

Test animals: adult females which have sucked themselves full

Solvent: dimethyl sulphoxide

20 mg of active substance are dissolved in 1 ml of dimethyl sulphoxide,and lesser concentrations are prepared by dilution with the samesolvent.

The test is carried out in 5 replications. 1 μl of the solutions isinjected into the abdomen, and the animals are transferred into dishesand kept in a controlled-environment cabinet. The activity is determinedvia the inhibition of oviposition. 100% means that no tick has depositedeggs.

In this test, an activity of 100% was shown, for example, by thecompound of Preparation Example (I-1-a-2) at an exemplary activecompound concentration of 20 μg/animal.

What is claimed is:
 1. A compound having the formula (II)

in which Q represents

A represents a respectively optionally substituted radical from thegroup consisting of alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl andalkylthioalkyl, represents respectively saturated or unsaturated andoptionally substituted cycloalkyl or heterocyclyl or representsrespectively optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-,halogenoalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,B represents alkyl or alkoxyalkyl or A and B together with the carbonatom that they are attached to represent a saturated or unsaturated,optionally substituted carbocycle or heterocycle, X represents halogen,alkyl, alkenyl, alkynyl, alkoxy, benzyloxy, halogenoalkyl,halogenoalkoxy, cyano or nitro, Z represents hydrogen, amino, halogen,alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro orrespectively optionally substituted phenoxy, phenylthio, 5- or6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy orphenylalkylthio, and R⁸ represents alkyl.
 2. The compound of claim 1having the formula

wherein Q represents

A represents a respectively optionally substituted radical from thegroup consisting of alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl andalkylthioalkyl, represents respectively saturated or unsaturated andoptionally substituted cycloalkyl or heterocyclyl or representsrespectively optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-,halogenoalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,B represents alkyl or alkoxyalkyl or A and B together with the carbonatom that they are attached to represent a saturated or unsaturated,optionally substituted carbocycle or heterocycle, X represents halogen,alkyl, alkenyl, alkynyl, alkoxy, benzyloxy, halogenoalkyl,halogenoalkoxy, cyano or nitro, Z represents hydrogen, amino, halogen,alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, hydroxyl, cyano, nitro orrespectively optionally substituted phenoxy, phenylthio, 5- or6-membered hetaryloxy, 5- or 6-membered hetarylthio, phenylalkyloxy orphenylalkylthio, and R⁸ represents alkyl.